TWI714101B - Surface treatment steel plate - Google Patents

Surface treatment steel plate Download PDF

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Publication number
TWI714101B
TWI714101B TW108118225A TW108118225A TWI714101B TW I714101 B TWI714101 B TW I714101B TW 108118225 A TW108118225 A TW 108118225A TW 108118225 A TW108118225 A TW 108118225A TW I714101 B TWI714101 B TW I714101B
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Taiwan
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coating film
coating
steel sheet
rust inhibitor
based alloy
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TW108118225A
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Chinese (zh)
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TW202003879A (en
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柴尾史生
平井亞希子
東新邦彥
河村保明
田浩平
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日商日本製鐵股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/04—Alloys based on zinc with aluminium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/12—Aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C—CHEMISTRY; METALLURGY
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    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
    • C—CHEMISTRY; METALLURGY
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    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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Abstract

本發明係關於一種表面處理鋼板，其特徵在於：具有鋼板、形成於鋼板之至少單面的Zn系合金鍍層及形成於Zn系合金鍍層上的塗膜，且該塗膜包含防鏽劑與黏結劑樹脂；並且，距離Zn系合金鍍層與塗膜之界面10nm之位置的前述塗膜中之防鏽劑的濃度係塗膜中之防鏽劑的平均濃度的1.5~5.0倍。The present invention relates to a surface-treated steel sheet, which is characterized by having a steel sheet, a Zn-based alloy coating layer formed on at least one side of the steel sheet, and a coating film formed on the Zn-based alloy coating layer, and the coating film includes a rust inhibitor and a bonding agent. Agent resin; And, the concentration of the anti-rust agent in the aforementioned coating film at a position 10nm away from the interface between the Zn-based alloy plating layer and the coating film is 1.5 to 5.0 times the average concentration of the anti-rust agent in the coating film.

Description

表面處理鋼板Surface treatment steel plate

發明領域 本發明係有關於耐蝕性佳之表面處理鋼板。Invention field The present invention relates to a surface-treated steel sheet with excellent corrosion resistance.

發明背景 已知有用於家電用、建材用、汽車用等之耐蝕性佳之各種鍍敷鋼板。例如已知有利用熔融鍍鋅等於鋼板上形成有鍍鋅層的鍍鋅鋼板。依上述將鍍鋅層設於鋼板上時，例如即便在鍍鋅鋼板損傷而鋼板露出時，較構成鋼板之鐵更易腐蝕之鋅會先腐蝕而形成保護皮膜，然後即可藉由該保護皮膜防止鋼板腐蝕。因此，鍍鋅鋼板擴展用於要求耐蝕性之各種用途上。Background of the invention Various coated steel sheets with excellent corrosion resistance are known for use in household appliances, building materials, automobiles, etc. For example, a galvanized steel sheet in which a galvanized layer is formed on the steel sheet using hot-dip galvanizing is known. When the galvanized layer is provided on the steel sheet as described above, for example, even when the galvanized steel sheet is damaged and the steel sheet is exposed, zinc, which is more corrosive than the iron constituting the steel sheet, will corrode first to form a protective film, and then the protective film can prevent Corrosion of steel plate. Therefore, galvanized steel sheets are widely used in various applications requiring corrosion resistance.

但，鍍鋅鋼板等各種鍍敷鋼板的表面卻有會因周邊環境而劣化之情形。例如鍍層因大氣中所含鹽分等電解質或於高溫多濕環境下存在之氧、水分而氧化，而有生成白鏽之問題。白鏽之生成會有損及外觀均勻性之虞，故要求鍍鋅鋼板要有更高的耐蝕性。However, the surface of various plated steel sheets such as galvanized steel sheets may deteriorate due to the surrounding environment. For example, the plating layer is oxidized due to electrolytes such as salt contained in the atmosphere or oxygen and moisture existing in a high temperature and humidity environment, and there is a problem of white rust formation. The generation of white rust may damage the appearance uniformity, so galvanized steel sheets are required to have higher corrosion resistance.

更提高鍍鋅鋼板之耐蝕性的技術已知有施有Zn-Al-Mg系合金鍍敷等之Zn系合金鍍敷鋼板。A technique for further improving the corrosion resistance of galvanized steel sheets is known as Zn-based alloy-plated steel sheets that are coated with Zn-Al-Mg-based alloys.

但，對於所述Zn系合金鍍敷鋼板還要求耐蝕性進一步的提升，尤其要求像是防止氧等腐蝕因子到達合金鍍層以確保優異耐蝕性之技術。並且，還要求在對所述合金鍍敷鋼板施行加工後仍可維持優異的耐蝕性。However, the corrosion resistance of the Zn-based alloy plated steel sheet is also required to be further improved. In particular, it is required to prevent corrosion factors such as oxygen from reaching the alloy plating layer to ensure excellent corrosion resistance. In addition, it is also required to maintain excellent corrosion resistance even after processing the alloy plated steel sheet.

專利文獻1中揭示了一種耐蝕性佳之鍍鋅鋼板，其包含：鋼板、形成於鋼板表面之Zn-Al-Mg系合金鍍層與形成於合金鍍層上之含鋁的皮膜。Patent Document 1 discloses a galvanized steel sheet with excellent corrosion resistance, which includes a steel sheet, a Zn-Al-Mg alloy coating layer formed on the surface of the steel sheet, and an aluminum-containing coating film formed on the alloy coating layer.

又，專利文獻2中揭示了一種表面處理金屬板，係於金屬板等具有至少一層塗膜層者，該表面處理金屬板之特徵在於：形成於最表面之塗膜層含有具陰離子性官能基的有機樹脂與選自Li等之至少1種陽離子性金屬元素，且靠近塗膜層外表面之區域有陽離子性金屬元素濃化；並闡示了所述表面處理鋼板不會使耐蝕性降低且可使耐鹼性、耐溶劑性提升。In addition, Patent Document 2 discloses a surface-treated metal plate that has at least one coating layer such as a metal plate. The surface-treated metal plate is characterized in that the coating layer formed on the outermost surface contains an anionic functional group. The organic resin and at least one cationic metal element selected from Li, etc., and the cationic metal element is concentrated in the area close to the outer surface of the coating layer; and it shows that the surface-treated steel plate will not reduce the corrosion resistance and It can improve alkali resistance and solvent resistance.

並且，專利文獻3中揭示了一種塗裝鋼板用基底處理組成物，其包含：特定的有機矽化合物、六氟金屬酸、具有特定陽離子性基之胺甲酸乙酯樹脂、釩化合物與水性介質；並闡示了藉由使用所述組成物可於鋼板上形成具有耐屋簷下耐蝕性之基底處理層。In addition, Patent Document 3 discloses a substrate treatment composition for coated steel sheets, which includes a specific organosilicon compound, a hexafluorometallic acid, a urethane resin with a specific cationic group, a vanadium compound, and an aqueous medium; And it is illustrated that by using the composition, a base treatment layer with corrosion resistance under the eaves can be formed on a steel plate.

專利文獻4~6則揭示了一種於鋅系鍍敷鋼板上具有例如包含釩系防鏽顏料之樹脂皮膜的塗裝鋼板。Patent Documents 4 to 6 disclose a coated steel sheet having, for example, a resin film containing a vanadium-based anticorrosive pigment on a zinc-based coated steel sheet.

先前技術文獻 專利文獻 專利文獻1：國際公開第2015/075792號 專利文獻2：日本特開2009-248460號公報 專利文獻3：日本特開2014-214315號公報 專利文獻4：日本特開2005-015834號公報 專利文獻5：日本特開2013-194145號公報 專利文獻6：日本特開2001-003181號公報Prior art literature Patent literature Patent Document 1: International Publication No. 2015/075792 Patent Document 2: Japanese Patent Application Publication No. 2009-248460 Patent Document 3: JP 2014-214315 A Patent Document 4: Japanese Patent Application Publication No. 2005-015834 Patent Document 5: Japanese Patent Application Publication No. 2013-194145 Patent Document 6: Japanese Patent Application Publication No. 2001-003181

發明概要 發明欲解決之課題 專利文獻1記載之鍍鋅鋼板係於鋼板上設置Zn-Al-Mg-Si合金鍍層，主要係藉由該合金鍍層確保鍍鋅鋼板之耐蝕性。又，專利文獻1闡示了可更於合金鍍層上之皮膜中添加防鏽劑，但未就皮膜中之防鏽劑的濃度分布或其控制方法充分檢討。因此，就專利文獻1記載之鍍鋅鋼板之耐蝕性提升仍有改善餘地。Summary of the invention Problems to be solved by the invention In the galvanized steel sheet described in Patent Document 1, a Zn-Al-Mg-Si alloy coating is provided on the steel sheet, and the corrosion resistance of the galvanized steel sheet is mainly ensured by the alloy coating. In addition, Patent Document 1 explains that it is possible to add a rust inhibitor to the film on the alloy plating layer, but it has not fully reviewed the concentration distribution of the rust inhibitor in the film or its control method. Therefore, the corrosion resistance of the galvanized steel sheet described in Patent Document 1 still has room for improvement.

又，專利文獻2記載之發明係有關於一種具有不會使耐蝕性降低且主要已提升了耐鹼性、耐溶劑性之皮膜的表面處理金屬板。而且並未就塗膜層中之陽離子性金屬元素的濃化程度進行充分檢討，因此關於專利文獻2記載之表面處理金屬板之耐蝕性提升仍有改善餘地。In addition, the invention described in Patent Document 2 relates to a surface-treated metal sheet having a coating film that does not reduce corrosion resistance and mainly has improved alkali resistance and solvent resistance. Moreover, the degree of concentration of the cationic metal element in the coating layer has not been fully reviewed. Therefore, there is still room for improvement regarding the improvement of the corrosion resistance of the surface-treated metal plate described in Patent Document 2.

並且，專利文獻3記載之組成物中，為了提升耐蝕性而使用了釩化合物，但未就使用該組成物而獲得之基底處理層中的釩化合物的濃度分布進行充分檢討，因此關於耐蝕性之提升仍有改善餘地。專利文獻4~6記載之發明亦同樣未就皮膜中之釩化合物等防鏽顏料的濃度分布進行充分檢討，因此關於耐蝕性之提升仍有改善餘地。In addition, the composition described in Patent Document 3 uses a vanadium compound in order to improve the corrosion resistance, but the concentration distribution of the vanadium compound in the base treatment layer obtained by using the composition has not been fully reviewed. Therefore, regarding the corrosion resistance There is still room for improvement. The inventions described in Patent Documents 4 to 6 also did not fully review the concentration distribution of anti-corrosive pigments such as vanadium compounds in the film, and therefore there is still room for improvement regarding the improvement of corrosion resistance.

因此，鑑於上述問題點，本發明目的在於針對Zn系合金鍍敷鋼板提供耐蝕性佳之表面處理鋼板。Therefore, in view of the above-mentioned problems, the object of the present invention is to provide a surface-treated steel sheet with good corrosion resistance for a Zn-based alloy plated steel sheet.

用以解決課題之手段 本發明人等發現為了獲得耐蝕性佳之表面處理鋼板，重要的是於形成於Zn系合金鍍層上之塗膜中含有防鏽劑，且將距離該Zn系合金鍍層與塗膜之界面10nm之位置的塗膜中之防鏽劑濃度設為塗膜中之防鏽劑平均濃度的1.5倍以上且5.0倍以下。亦即，根據本發明，在塗膜中之塗膜與Zn系合金鍍層之界面附近的區域，防鏽劑的存在相較於其他區域更濃。因此，藉由該防鏽劑的濃化區域可抑制氧等腐蝕因子通過塗膜而腐蝕Zn系合金鍍層。即，該防鏽劑的濃化區域可在塗膜中作為基底之Zn系合金鍍層的障蔽區域發揮作用。且，所述障蔽區域即便在對本發明表面處理鋼板施行加工後仍可充分發揮其作用。因此，具有所述塗膜之本發明表面處理鋼板可提供極佳之耐蝕性。Means to solve the problem The inventors found that in order to obtain a surface-treated steel sheet with good corrosion resistance, it is important that the coating film formed on the Zn-based alloy coating contains an anti-corrosion agent, and the distance from the interface between the Zn-based alloy coating and the coating is 10nm. The concentration of the rust inhibitor in the coating film is set to 1.5 times or more and 5.0 times the average concentration of the rust inhibitor in the coating film. That is, according to the present invention, in the area near the interface between the coating film and the Zn-based alloy plating layer in the coating film, the presence of the rust inhibitor is more concentrated than other areas. Therefore, the concentrated area of the rust inhibitor can prevent corrosion factors such as oxygen from corroding the Zn-based alloy plating layer through the coating film. That is, the concentrated area of the rust inhibitor can function as a barrier area of the Zn-based alloy plating layer as a base in the coating film. In addition, the barrier area can fully perform its function even after processing the surface-treated steel sheet of the present invention. Therefore, the surface-treated steel sheet of the present invention having the coating film can provide excellent corrosion resistance.

本發明即係鑑於上述見解而成者，其主旨如下。 (1) 一種表面處理鋼板，其特徵在於： 具有鋼板、形成於前述鋼板之至少單面的Zn系合金鍍層及形成於前述Zn系合金鍍層上的塗膜，且該塗膜包含防鏽劑與黏結劑樹脂； 前述Zn系合金鍍層之化學組成以質量%計為： Al：0.01~60%、 Mg：0.001~10%及 Si：0~2%；並且 距離前述Zn系合金鍍層與前述塗膜之界面10nm之位置的前述塗膜中之前述防鏽劑的濃度，係前述塗膜中之前述防鏽劑的平均濃度的1.5~5.0倍。 (2) 如(1)之表面處理鋼板，其中前述防鏽劑包含P、V及Mg中之至少1種。 (3) 如(1)或(2)之表面處理鋼板，其中前述塗膜中之前述防鏽劑的平均濃度以質量%計為3~15%。 (4) 如(1)至(3)中任一項之表面處理鋼板，其中前述塗膜更包含光亮顏料，且前述光亮顏料包含鋁及氧化物中之至少1種。 (5) 如(4)之表面處理鋼板，其中前述氧化物為氧化鋁、氧化矽、雲母、氧化鋯、氧化鈦、玻璃或氧化鋅。 (6) 如(4)或(5)之表面處理鋼板，其中前述光亮顏料更包含Rh、Cr、Ti、Ag及Cu中之至少1種。 (7) 如(4)至(6)中任一項之表面處理鋼板，其中前述塗膜中之前述光亮顏料的平均濃度以質量%計為5~15%。The present invention was made in view of the above findings, and its gist is as follows. (1) A surface-treated steel plate, which is characterized in: Having a steel plate, a Zn-based alloy coating layer formed on at least one side of the aforementioned steel plate, and a coating film formed on the aforementioned Zn-based alloy coating layer, and the coating film includes a rust inhibitor and a binder resin; The chemical composition of the aforementioned Zn series alloy coating is calculated as mass %: Al: 0.01~60%, Mg: 0.001~10% and Si: 0~2%; and The concentration of the rust inhibitor in the coating film at a position 10 nm away from the interface between the Zn-based alloy plating layer and the coating film is 1.5 to 5.0 times the average concentration of the rust inhibitor in the coating film. (2) The surface-treated steel sheet of (1), wherein the aforementioned rust inhibitor includes at least one of P, V, and Mg. (3) Such as (1) or (2) of the surface-treated steel sheet, wherein the average concentration of the aforementioned anti-rust agent in the aforementioned coating film is 3-15% by mass%. (4) The surface-treated steel sheet according to any one of (1) to (3), wherein the coating film further contains a bright pigment, and the bright pigment contains at least one of aluminum and an oxide. (5) Such as (4) the surface-treated steel sheet, wherein the aforementioned oxide is aluminum oxide, silicon oxide, mica, zirconium oxide, titanium oxide, glass or zinc oxide. (6) Such as the surface-treated steel sheet of (4) or (5), wherein the bright pigment further includes at least one of Rh, Cr, Ti, Ag and Cu. (7) The surface-treated steel sheet according to any one of (4) to (6), wherein the average concentration of the bright pigment in the coating film is 5-15% by mass%.

發明效果 根據本發明，於形成於Zn系合金鍍層上之塗膜中包含防鏽劑，且距離Zn系合金鍍層與塗膜之界面10nm之位置的防鏽劑之濃度係塗膜中之防鏽劑的平均濃度的1.5倍以上且5.0倍以下。亦即，在塗膜中之塗膜與Zn系合金鍍層之界面附近的區域，防鏽劑的存在相較於其他部分更濃。因此，該防鏽劑的濃化區域會作為Zn系合金鍍層防範氧等腐蝕因子之障蔽區域發揮作用，結果可提供耐蝕性佳之表面處理鋼板。且，根據本發明，在對本發明表面處理鋼板施行加工後仍可維持優異的耐蝕性。Invention effect According to the present invention, the coating film formed on the Zn alloy coating layer contains the rust inhibitor, and the concentration of the rust inhibitor at a position 10 nm away from the interface between the Zn alloy coating layer and the coating film is the same as that of the rust inhibitor in the coating film 1.5 times or more and 5.0 times or less the average concentration. That is, in the area near the interface between the coating film and the Zn-based alloy coating in the coating film, the presence of the rust inhibitor is more concentrated than other parts. Therefore, the concentrated area of the rust inhibitor acts as a barrier area for the Zn-based alloy coating to prevent corrosion factors such as oxygen, and as a result, a surface treated steel sheet with good corrosion resistance can be provided. In addition, according to the present invention, even after processing the surface-treated steel sheet of the present invention, excellent corrosion resistance can be maintained.

又，根據本發明，有Zn系合金鍍層上之塗膜中包含光亮顏料之情形。在所述情況時，藉由該光亮顏料之金屬外觀，本發明表面處理鋼板的亮度便可提升，而可提供設計性佳之表面處理鋼板。並且，塗膜中含光亮顏料時，例如即便Zn系合金鍍層因Zn系合金鍍層之鋅氧化等而變黑(以下記載為黑變)，仍可藉由塗膜中所含光亮顏料而使該黑變不被看見，亦即可抑制塗膜外觀上的變化而提供設計性佳之表面處理鋼板。Furthermore, according to the present invention, there are cases where bright pigments are included in the coating film on the Zn-based alloy plating layer. In this case, by the metallic appearance of the bright pigment, the brightness of the surface-treated steel sheet of the present invention can be improved, and a surface-treated steel sheet with good design can be provided. In addition, when a bright pigment is contained in the coating film, for example, even if the Zn-based alloy coating layer turns black due to zinc oxidation of the Zn-based alloy coating layer (hereinafter referred to as blackening), the bright pigment contained in the coating film can still make the coating The blackening is not visible, which can suppress the change in the appearance of the coating film and provide a surface-treated steel sheet with good design.

並且，根據本發明，係於形成塗膜時使用pH3.0~5.0之酸性塗料，故Zn系合金鍍層表面上之氧化被膜會被適當地去除，而Zn系合金鍍層與塗膜行化學結合，藉此於加工時可具有優異之密著性。又，根據本發明，藉由將塗料設為上述pH，可製作防鏽劑已穩定溶解之狀態的塗料，而可具有較鹼性塗料更佳之儲存穩定性。In addition, according to the present invention, an acid paint with a pH of 3.0 to 5.0 is used when forming the coating, so the oxide film on the surface of the Zn alloy coating is properly removed, and the Zn alloy coating is chemically combined with the coating. Therefore, it can have excellent adhesion during processing. Furthermore, according to the present invention, by setting the paint to the above pH, a paint in a state where the rust inhibitor has been stably dissolved can be produced, and it can have better storage stability than alkaline paint.

用以實施發明之形態 [表面處理鋼板] 本發明表面處理鋼板之特徵在於：具有鋼板、形成於鋼板之至少單面的Zn系合金鍍層及形成於Zn系合金鍍層上的塗膜，且該塗膜包含防鏽劑與黏結劑樹脂；並且前述Zn系合金鍍層之化學組成以質量%計為：Al：0.01~60%、Mg：0.001~10%及Si：0~2%；並且，距離Zn系合金鍍層與塗膜之界面10nm之位置的前述塗膜中之防鏽劑的濃度，係塗膜中之防鏽劑的平均濃度的1.5~5.0倍。以下就本發明表面處理鋼板的構成要件予以說明。The form used to implement the invention [Surface treatment steel plate] The surface-treated steel sheet of the present invention is characterized by having a steel sheet, a Zn-based alloy coating layer formed on at least one side of the steel sheet, and a coating film formed on the Zn-based alloy coating layer, and the coating film includes a rust inhibitor and a binder resin; and The chemical composition of the aforementioned Zn-based alloy coating is calculated by mass%: Al: 0.01~60%, Mg: 0.001~10%, and Si: 0~2%; and the distance from the interface between the Zn-based alloy coating and the coating is 10nm The concentration of the anti-rust agent in the aforementioned coating film is 1.5 to 5.0 times the average concentration of the anti-rust agent in the coating film. The constituent elements of the surface-treated steel sheet of the present invention will be described below.

>鋼板> 本發明之鋼板(鍍敷原板)無特別限定，可使用熱軋鋼板、冷軋鋼板等一般的鋼板。鋼種類亦無特別限定，例如可使用Al脫氧鋼、含有Ti、Nb等之極低碳鋼、及於該等中含有P、Si、Mn等元素之高張力鋼等。本發明之鋼板的板厚無特別限定，例如只要為0.25~3.5mm即可。>Steel Plate> The steel sheet (plated base sheet) of the present invention is not particularly limited, and general steel sheets such as hot-rolled steel sheets and cold-rolled steel sheets can be used. The type of steel is also not particularly limited. For example, Al deoxidized steel, very low carbon steel containing Ti, Nb, etc., and high-tensile steel containing elements such as P, Si, Mn, etc. can be used. The thickness of the steel plate of the present invention is not particularly limited, and it may be, for example, 0.25 to 3.5 mm.

>Zn系合金鍍層> 本發明之Zn系合金鍍層係形成於鋼板上。該Zn系合金鍍層可形成於鋼板單面亦可形成於兩面。Zn系合金鍍層可為至少含有Al與Mg之Zn-Al-Mg合金鍍層，且可為更含有Si之Zn-Al-Mg-Si合金鍍層。該等各含量(濃度)以質量%計為Al：0.01~60%、Mg：0.001~10%及Si：0~2%，且剩餘部分為Zn及不純物。以下，關於Zn系合金鍍層之化學組成僅記為「%」時，表示「質量%」。>Zn series alloy coating> The Zn alloy coating layer of the present invention is formed on the steel plate. The Zn-based alloy coating can be formed on one side of the steel sheet or on both sides. The Zn alloy plating layer may be a Zn-Al-Mg alloy plating layer containing at least Al and Mg, and may be a Zn-Al-Mg-Si alloy plating layer containing Si more. The contents (concentrations) are calculated by mass% as Al: 0.01-60%, Mg: 0.001-10%, and Si: 0-2%, and the remaining part is Zn and impurities. Hereinafter, when the chemical composition of the Zn-based alloy coating is only described as "%", it means "mass%".

Zn系合金鍍層之Al含量若少於0.01%，則無法充分發揮含有Al所得之提升鍍敷鋼板之耐蝕性的效果，而若多於60%，則使耐蝕性提升之效果會達飽和。因此，Al含量為0.01%以上，例如可為0.1%以上、0.5%以上、1%以上、3%以上或5%以上，且為60%以下，例如可為55%以下、50%以下、40%以下或30%以下。較佳Al含量為1~60%，更宜為5~60%。If the Al content of the Zn alloy coating is less than 0.01%, the effect of improving the corrosion resistance of the plated steel sheet obtained by containing Al cannot be fully exerted, and if it is more than 60%, the effect of improving the corrosion resistance will be saturated. Therefore, the Al content is 0.01% or more, for example, it can be 0.1% or more, 0.5% or more, 1% or more, 3% or more or 5% or more, and 60% or less, for example, it can be 55% or less, 50% or less, 40%. % Or less or 30% or less. The Al content is preferably 1-60%, more preferably 5-60%.

Zn系合金鍍層之Mg含量若少於0.001%，則有無法充分發揮含有Mg所得之提升鍍敷鋼板之耐蝕性的效果的情形。另一方面，若多於10%則鍍敷浴中Mg會無法完全溶解而以氧化物狀態懸浮(一般稱為浮渣)，當在該鍍敷浴中進行鍍鋅時，氧化物即會附著於鍍敷表層造成外觀不良，或有產生沒鍍敷到的部分(一般稱為未鍍)之虞。因此，Mg含量為0.001%以上，例如可為0.01%以上、0.1%以上、0.5%以上、1%以上或2%以上，且為10%以下，例如可為8%以下、6%以下、5%以下或4%以下。Mg含量宜為1~5%，更宜為1~4%。If the Mg content of the Zn-based alloy coating is less than 0.001%, the effect of improving the corrosion resistance of the coated steel sheet obtained by containing Mg may not be fully exhibited. On the other hand, if it is more than 10%, Mg will not be completely dissolved in the plating bath and will be suspended in an oxide state (generally called dross). When zinc plating is carried out in the plating bath, the oxide will adhere It may cause poor appearance on the surface of the plating, or may produce unplated parts (generally called unplated). Therefore, the Mg content is 0.001% or more, for example, it can be 0.01% or more, 0.1% or more, 0.5% or more, 1% or more, or 2% or more, and 10% or less, for example, it can be 8% or less, 6% or less, 5 % Or less or 4% or less. The Mg content should be 1~5%, more preferably 1~4%.

Zn系合金鍍層之Si含量的下限可為0%，惟為使Zn系合金鍍層的耐蝕更提升，宜設為0.001%~2%。Si含量例如可為0.005%以上、0.01%以上、0.05%以上、0.1%以上或0.5%以上，且可為1.8%以下、1.5%以下或1.2%以下。Si含量宜為0.1~2%，更宜為0.5~1.5%。The lower limit of the Si content of the Zn alloy coating can be 0%, but in order to improve the corrosion resistance of the Zn alloy coating, it should be set to 0.001%~2%. The Si content can be 0.005% or more, 0.01% or more, 0.05% or more, 0.1% or more, or 0.5% or more, and can be 1.8% or less, 1.5% or less, or 1.2% or less, for example. The Si content should be 0.1~2%, more preferably 0.5~1.5%.

本發明之Zn系合金鍍層可利用熔融鍍敷或蒸鍍等公知鍍敷方法來形成。例如Zn系合金鍍層的厚度只要為1~30μm即可。The Zn-based alloy plating layer of the present invention can be formed by a known plating method such as hot-dip plating or vapor deposition. For example, the thickness of the Zn-based alloy plating layer may be 1-30 μm.

>塗膜> 本發明之塗膜係形成於Zn系合金鍍層上。塗膜中包含防鏽劑與黏結劑樹脂。為了使表面處理鋼板的亮度提升，宜更於塗膜中含有光亮顏料即可。本發明表面處理鋼板之塗膜中，防鏽劑係以微細化合物(例如P化合物或V化合物)狀態存在。如所述為了使防鏽劑在塗膜中以微細化合物狀態存在，且如上述於塗膜與Zn系合金鍍層之界面區域形成防鏽劑的濃化區域，有效的是於用以形成本發明之塗膜的塗料使用例如pH3.0~5.0之酸性塗料。此外，防鏽劑係在塗膜中細微地分散，故以一般分析方法難以在塗膜中明確區分微細的防鏽劑與用以形成塗膜之黏結劑樹脂並加以特定，而會觀測為防鏽劑與黏結劑樹脂在塗膜中係分布在相同區域中。因此，本發明中，於塗膜中「包含防鏽劑」係指將構成上述微細化合物且可發揮防鏽機能之元素、例如P、V、Mg之元素含於塗膜中。因此，後述防鏽劑之「濃度」係指例如P、V、Mg之元素濃度(含量)之合計，且其單位設為質量%。>Coating> The coating film of the present invention is formed on the Zn alloy plating layer. The coating film contains rust inhibitor and binder resin. In order to increase the brightness of the surface-treated steel sheet, it is better to include bright pigments in the coating film. In the coating film of the surface-treated steel sheet of the present invention, the rust inhibitor exists in the state of a fine compound (for example, a P compound or a V compound). In order to make the rust inhibitor exist in the coating film as a fine compound as described above, and to form a concentrated area of the rust inhibitor in the interface area between the coating film and the Zn-based alloy plating layer as described above, it is effective to form the present invention The coating of the coating film uses, for example, an acidic paint with a pH of 3.0 to 5.0. In addition, the rust inhibitor is finely dispersed in the coating film, so it is difficult to clearly distinguish between the fine rust inhibitor and the binder resin used to form the coating film in the coating film by general analysis methods. The rust agent and the binder resin are distributed in the same area in the coating film. Therefore, in the present invention, "containing a rust inhibitor" in the coating film means that elements constituting the above-mentioned fine compound and exhibiting a rust preventive function, such as elements of P, V, and Mg, are contained in the coating film. Therefore, the "concentration" of the rust inhibitor mentioned later refers to, for example, the sum of the element concentrations (content) of P, V, and Mg, and the unit is mass %.

如所述將用以形成本發明之塗膜的塗料設為例如pH3.0~5.0之酸性，可使防鏽劑成分在塗料中以已溶解之狀態存在。亦即，本發明之防鏽劑的成分並不是以化合物狀態(即固體成分)含於塗料中，而是以離子狀態(即溶解成分)含於塗料中。因此，將所述塗料塗佈於Zn系合金鍍層表面並使其硬化，可使防鏽劑在已形成之塗膜中以微細化合物狀態略均勻地存在。As described above, the paint used to form the coating film of the present invention is made acidic, for example, with a pH of 3.0 to 5.0, so that the rust inhibitor component can exist in the paint in a dissolved state. That is, the components of the rust inhibitor of the present invention are not contained in the paint in a compound state (that is, solid content), but are contained in the paint in an ionic state (that is, a dissolved component). Therefore, by applying the coating to the surface of the Zn-based alloy plating layer and hardening it, the rust inhibitor can be slightly uniformly present in the formed coating film as a fine compound.

且將pH3.0~5.0之酸性塗料塗佈於Zn系合金鍍層表面時，該酸性塗料會去除Zn系合金鍍層表面上的氧化被膜，而在Zn系合金鍍層之表面附近，離子狀態的防鏽劑成分會與Zn系合金鍍層中的成分進行反應。結果在使塗料硬化後，可於Zn系合金鍍層與塗膜之界面附近形成反應產物濃化的區域。因此，於塗膜中在所述反應產物存在之區域中，防鏽劑不僅有在塗膜中略均勻存在之微細化合物還有如上述形成之反應產物存在，故防鏽劑(例如P、V、Mg)相較於其他區域更濃化，結果該濃化區域可在塗膜中作為防止腐蝕因子入侵之障蔽區域發揮作用。因此，使用pH3.0~5.0之酸性塗料製出之本發明表面處理鋼板於Zn系合金鍍層與塗膜之界面附近具有防鏽劑之濃化區域，而可提供極高耐蝕性。And when the acid paint with pH 3.0~5.0 is applied to the surface of the Zn-based alloy coating, the acidic paint will remove the oxide film on the surface of the Zn-based alloy coating, and near the surface of the Zn-based alloy coating, the ionic state prevents rust The composition of the agent reacts with the composition of the Zn-based alloy coating. As a result, after the coating is hardened, a region where the reaction product is concentrated can be formed near the interface between the Zn-based alloy plating layer and the coating film. Therefore, in the coating film in the area where the reaction product exists, the rust inhibitor not only has fine compounds that are slightly uniformly present in the coating film, but also the reaction product formed as described above, so the rust inhibitor (such as P, V, Mg ) Is more concentrated than other areas, and as a result, the concentrated area can function as a barrier area to prevent the invasion of corrosive factors in the coating film. Therefore, the surface-treated steel sheet of the present invention made by using the acid paint of pH 3.0-5.0 has a concentrated area of rust inhibitor near the interface between the Zn-based alloy plating layer and the coating film, and can provide extremely high corrosion resistance.

塗膜的平均厚度無特別限定，例如可為3~15μm。藉由為所述範圍之塗膜的平均厚度，塗膜便能發揮充分抑制基底之Zn系合金鍍層腐蝕之障蔽功能，而可對本發明表面處理鋼板提供充分的耐蝕性。且，塗膜的平均厚度只要為上述範圍，則即便對具有所述塗膜之本發明表面處理鋼板施行加工亦不會於塗膜產生龜裂等，而可提供加工性亦佳之塗膜。The average thickness of a coating film is not specifically limited, For example, it can be 3-15 micrometers. By having the average thickness of the coating film in the above-mentioned range, the coating film can exhibit a barrier function of sufficiently inhibiting the corrosion of the Zn-based alloy coating of the base, and can provide sufficient corrosion resistance to the surface-treated steel sheet of the present invention. In addition, as long as the average thickness of the coating film is within the above range, even if the surface-treated steel sheet of the present invention having the coating film is processed, cracks and the like are not generated in the coating film, and a coating film with excellent workability can be provided.

塗膜的平均厚度若小於3μm，則為了充分抑制基底之Zn系合金鍍層腐蝕的進行有厚度不充分的情形，因此本發明表面處理鋼板之耐蝕性有不充分之虞。另一方面，塗膜的平均厚度大於15μm時，增加塗膜厚度所帶來之增加耐蝕性的效果會變小，且硬化亦耗時，而在成本面有不利之虞。且當塗膜過厚，對具有塗膜之鋼板施行彎曲等加工時會有於塗膜產生龜裂之虞，而有使本發明表面處理鋼板之加工性降低之虞。塗膜的平均厚度例如可為3μm以上、4μm以上或5μm以上，且可為12μm以下或10μm以下。因此，塗膜的平均厚度宜為3μm以上且12μm以下，且宜為5μm以上且10μm以下。If the average thickness of the coating film is less than 3 μm, the thickness may be insufficient in order to sufficiently suppress the corrosion of the Zn-based alloy coating of the base, and therefore the corrosion resistance of the surface-treated steel sheet of the present invention may be insufficient. On the other hand, when the average thickness of the coating film is greater than 15 μm, the effect of increasing the thickness of the coating film to increase the corrosion resistance will be reduced, and curing will also take time, which may be disadvantageous in terms of cost. In addition, when the coating film is too thick, the coating film may be cracked when bending or other processing is performed on the coated steel sheet, and the workability of the surface-treated steel sheet of the present invention may decrease. The average thickness of the coating film can be, for example, 3 μm or more, 4 μm or more, or 5 μm or more, and can be 12 μm or less or 10 μm or less. Therefore, the average thickness of the coating film is preferably 3 μm or more and 12 μm or less, and preferably 5 μm or more and 10 μm or less.

本發明之塗膜的「平均厚度」可以當業者公知之任意方法決定。例如可以以下方法決定：觀察具有塗膜之鋼板的截面，並測定分別從Zn系合金鍍層與塗膜之界面上任意5處位置至塗膜表面之最短距離(即在與界面垂直之方向上測定距離)後，將該等測定值平均化來決定。The "average thickness" of the coating film of the present invention can be determined by any method known to the industry. For example, it can be determined by the following method: Observe the cross-section of the coated steel sheet, and measure the shortest distance from any five positions on the interface between the Zn-based alloy coating and the coated film to the surface of the coated film (ie, measured in the direction perpendicular to the interface After the distance), the measured values are averaged and determined.

(黏結劑樹脂) 作為本發明之塗膜成分使用之黏結劑樹脂只要為可在酸性溶劑中使用之樹脂即無特別限定，例如可為聚酯樹脂、胺甲酸乙酯樹脂或丙烯酸樹脂。黏結劑樹脂之硬化劑只要為可在酸性溶劑中使用且可使上述黏結劑樹脂硬化者即無特別限定，例如可使用三聚氰胺樹脂、異氰酸酯樹脂或環氧樹脂等。較佳的是本發明之黏結劑樹脂為聚酯樹脂，硬化劑為三聚氰胺樹脂。又，聚酯樹脂宜為具有-20~70℃之玻璃轉移溫度Tg與3000~30000之平均分子量者。黏結劑樹脂為胺甲酸乙酯樹脂時，宜為Tg為0~50℃且數量平均分子量為5000~25000者。黏結劑樹脂為丙烯酸樹脂時，宜為Tg為0~50℃且數量平均分子量為3000~25000者。(Binder resin) The binder resin used as the coating film component of the present invention is not particularly limited as long as it is a resin that can be used in an acidic solvent, and may be, for example, a polyester resin, a urethane resin, or an acrylic resin. The curing agent of the binder resin is not particularly limited as long as it can be used in an acid solvent and can harden the aforementioned binder resin. For example, melamine resin, isocyanate resin, epoxy resin, etc. can be used. Preferably, the binder resin of the present invention is a polyester resin, and the hardener is a melamine resin. In addition, the polyester resin preferably has a glass transition temperature Tg of -20 to 70°C and an average molecular weight of 3000 to 30,000. When the binder resin is a urethane resin, it should preferably have a Tg of 0-50°C and a number average molecular weight of 5000-25000. When the binder resin is acrylic resin, it should preferably have a Tg of 0-50°C and a number average molecular weight of 3000-25000.

(防鏽劑) 為了提升本發明表面處理鋼板之耐蝕性，使防鏽劑(典型上為P及/或V)含於塗膜中。本發明之防鏽劑如上述在塗膜中係以微細化合物狀態略均勻地存在，在本發明中，「防鏽劑」係指構成防鏽劑且可發揮防鏽機能之元素，例如P元素、V元素、Mg元素。如所述於塗膜中以微細化合物狀態存在之防鏽劑可溶於水，故塗膜暴露於例如濕潤環境下時，塗膜中之防鏽劑會溶於水而溶出防鏽劑成分，而可發揮抑制Zn系合金鍍層腐蝕之防鏽機能。且如上述，Zn系合金鍍層與塗膜之界面附近的濃化區域中，形成了防鏽劑成分(例如P、V等)與Zn系合金鍍層中之成分的反應產物，該反應產物存在之區域會發揮腐蝕因子之障蔽區域之作用。因此，本發明之表面處理鋼板因防鏽劑在塗膜中以微細化合物狀態存在，且於Zn系合金鍍層與塗膜之界面區域具有防鏽劑的濃化區域，故具有優異之耐蝕性。(Rust inhibitor) In order to improve the corrosion resistance of the surface-treated steel sheet of the present invention, a rust inhibitor (typically P and/or V) is contained in the coating film. The rust inhibitor of the present invention is slightly uniformly present in the coating film in the state of fine compounds as described above. In the present invention, the "rust inhibitor" refers to an element that constitutes the rust inhibitor and can exert rust prevention functions, such as P element , V element, Mg element. As mentioned, the rust inhibitor in the form of fine compounds in the coating film is soluble in water. Therefore, when the coating film is exposed to, for example, a humid environment, the rust inhibitor in the coating film will dissolve in water to dissolve the rust inhibitor component. And can exert the anti-rust function of inhibiting the corrosion of Zn alloy coating. And as mentioned above, in the concentrated area near the interface between the Zn-based alloy coating and the coating film, a reaction product of the rust inhibitor component (such as P, V, etc.) and the components in the Zn-based alloy coating is formed. The area will act as a barrier area for corrosive factors. Therefore, the surface-treated steel sheet of the present invention has excellent corrosion resistance because the rust inhibitor is present in the coating film as a fine compound, and the interface area between the Zn-based alloy plating layer and the coating film has a concentrated area of the rust inhibitor.

可添加於形成包含本發明防鏽劑之塗膜的塗料中之化合物(以下記載為防鏽劑源)可使用可溶解於酸性塗料之任意化合物。在所述酸性塗料中溶解之防鏽劑有時稱為陽離子抑制劑。The compound that can be added to the paint that forms the coating film containing the rust inhibitor of the present invention (hereinafter referred to as the rust inhibitor source) can be any compound that is soluble in acid paint. The rust inhibitor dissolved in the acid paint is sometimes called a cationic inhibitor.

本發明之防鏽劑源可舉如P(磷)化合物、V(釩)化合物及Mg(鎂)化合物。較佳的是於本發明之塗膜中單獨或組合含有P及V。更佳的是於塗膜中單獨含有P或組合含有P與V。The source of the rust inhibitor of the present invention may include P (phosphorus) compounds, V (vanadium) compounds and Mg (magnesium) compounds. Preferably, the coating film of the present invention contains P and V alone or in combination. It is more preferable to contain P alone or in combination with P and V in the coating film.

於塗膜中作為防鏽劑含有P時，尤可使加工部耐蝕性提升。加工部耐蝕性係指對具有塗膜之鋼板施行加工(例如彎曲加工)後之在該加工部的耐蝕性。如所述於塗膜中含有P而可提升加工部耐蝕性之理由，吾等認為係因具有以下效果之故：P與Zn系合金鍍層表面進行反應而形成磷酸鹽層，使加工部鈍化之效果；P本身形成難溶性塗膜而對腐蝕因子發揮障蔽性之效果；及，P會補足從基底金屬板溶出之金屬離子並與金屬離子一同形成難溶性化合物，而發揮障蔽性之效果。本發明之包含P之防鏽劑源並無特別限定，例如可舉正磷酸、偏磷酸、焦磷酸、三磷酸、四磷酸等磷酸類與磷酸三銨、磷酸氫二銨等銨鹽、Na、Mg、Al、K、Ca、Mn、Ni、Zn、Fe等之金屬鹽、胺基三(亞甲基膦酸)、1-羥基亞乙基-1,1-二膦酸、乙二胺四(亞甲基膦酸)、二伸乙三胺五(亞甲基膦酸)等膦酸類及其等之鹽、植酸等有機磷酸類及其等之鹽等。該等防鏽劑源可單獨或組合添加於用以形成本發明之塗膜的塗料中。When P is contained as a rust inhibitor in the coating film, the corrosion resistance of the processed part can be particularly improved. The corrosion resistance of the processed portion refers to the corrosion resistance of the processed portion after processing (for example, bending) of the coated steel sheet. As mentioned, the reason why P in the coating film can improve the corrosion resistance of the processed part is due to the following effects: P reacts with the surface of the Zn-based alloy coating to form a phosphate layer, which makes the processed part passivate. Effect: P itself forms a poorly soluble coating film and exerts a barrier effect on corrosion factors; and, P will supplement the metal ions eluted from the base metal plate and form a poorly soluble compound together with the metal ions to exert the barrier effect. The source of the rust inhibitor containing P of the present invention is not particularly limited. For example, phosphoric acids such as orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid, and ammonium salts such as triammonium phosphate and diammonium phosphate, Na, Metal salts of Mg, Al, K, Ca, Mn, Ni, Zn, Fe, etc., amino tris (methylene phosphonic acid), 1-hydroxyethylene-1,1-diphosphonic acid, ethylene diamine tetra (Methylene phosphonic acid), ethylene triamine penta (methylene phosphonic acid) and other phosphonic acids and their salts, phytic acid and other organic phosphoric acids and their salts, etc. These sources of rust inhibitors can be added to the paint used to form the coating film of the present invention alone or in combination.

又，於塗膜中作為防鏽劑包含V時，尤可使端面部耐蝕性提升。端面部耐蝕性係指例如對具有塗膜之鋼板施行加工(例如裁切加工)後之在該端面部的耐蝕性。如所述於塗膜中含有V而可提升端面部耐蝕性之理由，吾等認為係因於端面部從塗膜溶出之V會與從Zn系合金鍍層溶出之Zn或Al進行反應而形成腐蝕產物，使Zn系合金鍍層之表層鈍化，藉此可抑制腐蝕進行。本發明之含V的防鏽劑源可舉五氧化釩、偏釩酸HVO3 、偏釩酸銨、三氯氧釩VOCl3 、三氧化釩V2 O3 、二氧化釩、硫酸氧釩VOSO4 、乙醯丙酮氧釩VO(OC(＝CH2 )CH2 COCH3 )3 、乙醯丙酮釩V(OC(＝CH2 )CH2 COCH3 )3 、三氯化釩VCl3 等。該等防鏽劑源可單獨或組合添加於用以形成本發明之塗膜的塗料中。In addition, when V is contained as a rust inhibitor in the coating film, the corrosion resistance of the end surface can be improved particularly. The end surface corrosion resistance refers to, for example, the corrosion resistance on the end surface after processing (for example, cutting) a steel plate with a coating film. As mentioned above, the reason why the coating film contains V can improve the corrosion resistance of the end face. We believe that the V eluted from the coating film on the end face reacts with the Zn or Al eluted from the Zn alloy coating to form corrosion. The product passivates the surface layer of the Zn alloy coating, thereby inhibiting the progress of corrosion. The V-containing anti-rust agent source of the present invention can include vanadium pentoxide, metavanadate HVO 3 , ammonium metavanadate, vanadium trichloride VOCl 3 , vanadium trioxide V 2 O 3 , vanadium dioxide, vanadyl sulfate VOSO 4. Vanadium acetone VO(OC(=CH 2 )CH 2 COCH 3 ) 3 , vanadium acetone V(OC(=CH 2 )CH 2 COCH 3 ) 3 , vanadium trichloride VCl 3 and the like. These sources of rust inhibitors can be added to the paint used to form the coating film of the present invention alone or in combination.

本發明之含Mg的防鏽劑源可舉硝酸鎂Mg(NO3 )2 、硫酸鎂MgSO4 、乙酸鎂Mg(CH3 COO)2 等。該等防鏽劑源可單獨或組合添加於用以形成本發明之塗膜的塗料中。Mg與前述V同樣地可使端面部耐蝕性提升。吾等認為端面部耐蝕性提升之理由亦與V相同。The source of the Mg-containing rust inhibitor of the present invention may include magnesium nitrate Mg(NO 3 ) 2 , magnesium sulfate MgSO 4 , magnesium acetate Mg(CH 3 COO) 2 and the like. These sources of rust inhibitors can be added to the paint used to form the coating film of the present invention alone or in combination. Mg can improve the corrosion resistance of the end face similarly to the aforementioned V. We believe that the reason for the improvement of the end face corrosion resistance is the same as that of V.

塗膜中之防鏽劑的平均濃度以質量%計可為3~15%。此外，如上述，「防鏽劑的平均濃度」係基於塗膜中之例如P、V、Mg之元素的濃度(質量%)合計而得者。藉由為所述範圍之塗膜中之防鏽劑的平均濃度，可於塗膜整體中存在充分的防鏽劑，故可對本發明表面處理鋼板提供充分的耐蝕性。又，如上述即便防鏽劑於塗膜與Zn系合金鍍層之界面附近濃化，在其他區域中亦無防鏽劑的濃度不足之情形，而可對塗膜整體、亦即本發明表面處理鋼板提供充分的耐蝕性。The average concentration of rust inhibitor in the coating film can be 3-15% in terms of mass%. In addition, as mentioned above, the "average concentration of rust inhibitor" is based on the sum of the concentrations (mass %) of elements such as P, V, and Mg in the coating film. By being the average concentration of the rust inhibitor in the coating film within the above-mentioned range, a sufficient rust inhibitor can exist in the entire coating film, and therefore, sufficient corrosion resistance can be provided to the surface-treated steel sheet of the present invention. Moreover, as described above, even if the rust inhibitor is concentrated near the interface between the coating film and the Zn-based alloy coating, there is no insufficient concentration of the rust inhibitor in other areas, and the entire coating film, that is, the surface treatment of the present invention The steel plate provides sufficient corrosion resistance.

塗膜中之防鏽劑的平均濃度以質量%計小於3%時，塗膜整體中之防鏽劑的濃度會不足，而防鏽劑效果所帶來之耐蝕性的提升有限，從而有無法獲得充分的耐蝕性之虞。另一方面，塗膜中之防鏽劑的平均濃度若大於15%，則添加防鏽劑所帶來之耐蝕性提升的效果會飽和，而於成本上不佳。塗膜中之防鏽劑的平均濃度以質量%計可為5%以上、7%以上或10%以上，進而宜為5%以上且15%以下，且宜為7%以上且15%以下，更宜為10%以上且15%以下。When the average concentration of the rust inhibitor in the coating film is less than 3% in terms of mass%, the concentration of the rust inhibitor in the entire coating film will be insufficient, and the improvement of the corrosion resistance caused by the effect of the rust inhibitor is limited, so it is impossible Sufficient corrosion resistance may be obtained. On the other hand, if the average concentration of the rust inhibitor in the coating film is greater than 15%, the effect of improving the corrosion resistance brought by the addition of the rust inhibitor will be saturated, and the cost is not good. The average concentration of the rust inhibitor in the coating film can be 5% or more, 7% or more or more than 10% in terms of mass%, and more preferably 5% or more and 15% or less, and preferably 7% or more and 15% or less, More preferably, it is more than 10% and less than 15%.

在本說明書中使用之情況，「塗膜中之防鏽劑的平均濃度」係以以下方法決定。首先，以TEM觀察具有塗膜之鋼板的截面，並從塗膜表面上隨機選出之位置於與塗膜表面垂直之方向(厚度方向)上往Zn系合金鍍層劃出直線。然後，於該直線上將塗膜厚度分成11等分，分割出11個區域。並在從該區域中排除最靠近Zn系合金鍍層之區域後的塗膜中之10個區域中測定防鏽劑的濃度，亦即測定例如P、V、Mg之元素的濃度合計，並將該等測定值平均化來決定。各位置之防鏽劑濃度的測定可使用SEM或TEM所附能量分散型X射線分光器(EDS)進行元素分析來求得。When used in this manual, the "average concentration of rust inhibitor in the coating film" is determined by the following method. First, observe the cross-section of the coated steel sheet with TEM, and draw a straight line from the position on the coated film surface in the direction perpendicular to the coated film surface (thickness direction) to the Zn-based alloy coating. Then, the coating film thickness is divided into 11 equal parts on the straight line, and 11 regions are divided. The concentration of the rust inhibitor is measured in 10 areas of the coating film after excluding the area closest to the Zn-based alloy coating from the area, that is, the concentration of elements such as P, V, and Mg is measured, and the Wait until the measured values are averaged to determine. The concentration of the rust inhibitor at each position can be determined by elemental analysis using an energy dispersive X-ray spectrometer (EDS) attached to the SEM or TEM.

本發明中，距離Zn系合金鍍層與塗膜之界面10nm之位置的塗膜中之防鏽劑的濃度係塗膜中之防鏽劑的平均濃度的1.5倍以上且5.0倍以下。亦即，在塗膜中之塗膜與Zn系合金鍍層之界面附近的區域有防鏽劑濃化。如上述使防鏽劑於塗膜與Zn系合金鍍層之界面附近之區域相較於其他部分更濃化時，該防鏽劑的濃化區域可作為Zn系合金鍍層對氧等腐蝕因子障蔽之障蔽區域發揮作用。因此，可將腐蝕因子侵蝕Zn系合金鍍層之情形抑制到最小限度，從而表面處理鋼板可具有極佳之耐蝕性。且，藉由上述之防鏽劑的濃化區域，即便對表面處理鋼板施行加工後仍可充分地維持耐蝕性。In the present invention, the concentration of the rust inhibitor in the coating film at a position 10 nm from the interface between the Zn-based alloy plating layer and the coating film is 1.5 times to 5.0 times the average concentration of the rust inhibitor in the coating film. That is, the rust inhibitor is concentrated in the area near the interface between the coating film and the Zn-based alloy plating layer in the coating film. As mentioned above, when the area near the interface between the coating film and the Zn-based alloy coating is made more concentrated than other parts, the concentrated area of the rust-preventive agent can be used as a barrier for the Zn-based alloy coating to oxygen and other corrosion factors. The barrier area comes into play. Therefore, the corrosion of the Zn-based alloy coating by corrosion factors can be suppressed to a minimum, so that the surface-treated steel sheet can have excellent corrosion resistance. In addition, the above-mentioned concentrated area of the rust inhibitor can maintain sufficient corrosion resistance even after processing the surface-treated steel sheet.

當該值小於1.5倍，於塗膜中之塗膜與Zn系合金鍍層側之界面附近，作為抑制腐蝕因子通過而腐蝕Zn系合金鍍層之障蔽區域的效果會變弱，而有腐蝕因子到達Zn系合金鍍層之情形，從而有塗膜無法提供充分耐蝕性的情形。另一方面，該值大於5.0倍時，防鏽劑的濃化區域之濃化的程度會過高，故將表面處理鋼板加工後於防鏽劑的濃化區域會有塗膜內聚破壞之情形。如此一來，加工密著性會降低，結果有無法維持在加工部之耐蝕性而耐蝕性不充分之虞。距離Zn系合金鍍層與塗膜之界面10nm之位置的塗膜中之防鏽劑的濃度可為塗膜中之防鏽劑的平均濃度的1.7倍以上、2.0倍以上或2.2倍以上，且可為4.8倍以下、4.5倍以下、4.2倍以下、4.0倍以下或3.5倍以下，而宜為2.0倍以上且4.5倍以下，更宜為2.0倍以上且4.0倍以下，且2.5倍以上且4.0倍以下更佳。When the value is less than 1.5 times, near the interface between the coating film in the coating and the side of the Zn alloy coating, the effect of inhibiting the passage of corrosion factors and corroding the barrier area of the Zn alloy coating will be weakened, and the corrosion factors will reach Zn In the case of alloy plating, there are cases where the coating film cannot provide sufficient corrosion resistance. On the other hand, when the value is greater than 5.0 times, the concentration of the anti-rust agent will be too high. Therefore, after the surface-treated steel sheet is processed, the coating film will be damaged in the concentrated area of the anti-rust agent. situation. As a result, the processing adhesion will be reduced, and as a result, the corrosion resistance in the processed part may not be maintained and the corrosion resistance may be insufficient. The concentration of the rust inhibitor in the coating film at a position 10nm away from the interface between the Zn-based alloy coating and the coating film can be 1.7 times, 2.0 times, or 2.2 times the average concentration of the rust inhibitor in the coating film. 4.8 times or less, 4.5 times or less, 4.2 times or less, 4.0 times or less, or 3.5 times or less, preferably 2.0 times or more and 4.5 times or less, more preferably 2.0 times or more and 4.0 times or less, and 2.5 times or more and 4.0 times or less The following is better.

「距離Zn系合金鍍層與塗膜之界面10nm之位置的塗膜中之防鏽劑的濃度」係使用TEM-EDS從具有塗膜之鋼板的截面決定。具體上，係從觀察到的截面的TEM影像，於隨機選擇出之從Zn系合金鍍層與塗膜之界面於垂直方向上向塗膜表面距離10nm之5處位置利用TEM-EDS測定防鏽劑的濃度(即，例如P、V、Mg之元素的合計濃度)，並將該等測定值平均化來決定。"The concentration of the rust inhibitor in the coating film at a position 10nm away from the interface between the Zn-based alloy coating and the coating film" is determined from the cross section of the coated steel sheet using TEM-EDS. Specifically, from the TEM image of the observed cross-section, the rust inhibitor was measured by TEM-EDS at 5 positions at a distance of 10nm from the interface between the Zn-based alloy coating and the coating film in the vertical direction to the surface of the coating film randomly selected. The concentration of (ie, the total concentration of elements such as P, V, and Mg) is determined by averaging these measured values.

如前述pH3.0~5.0之酸性塗料為了去除Zn系合金鍍層表面上之氧化被膜，本發明之塗膜中所含防鏽劑成分(例如P)與Zn系合金鍍層所含成分(例如Zn)會在塗膜與Zn系合金鍍層之界面附近進行反應，而於該界面附近之區域形成反應產物(例如含Zn與P之反應產物)。於該反應產物存在之區域中，存在有與其他區域相同地在塗膜中均勻分散之防鏽劑成分和構成反應產物之防鏽劑成分兩者。因此，本發明表面處理鋼板中，在塗膜中之塗膜與Zn系合金鍍層之界面附近的區域，防鏽劑(例如P)的存在相較於其他區域更濃。In order to remove the oxide film on the surface of the Zn alloy coating, the acid paint with pH 3.0~5.0 mentioned above, the rust inhibitor component (such as P) contained in the coating film of the present invention and the component (such as Zn) contained in the Zn alloy coating The reaction occurs near the interface between the coating film and the Zn-based alloy coating, and reaction products (for example, reaction products containing Zn and P) are formed in the area near the interface. In the region where the reaction product exists, there are both the rust inhibitor component uniformly dispersed in the coating film as in the other regions and the rust inhibitor component constituting the reaction product. Therefore, in the surface-treated steel sheet of the present invention, in the area near the interface between the coating film and the Zn-based alloy plating layer in the coating film, the presence of the rust inhibitor (for example, P) is more concentrated than other areas.

所述反應產物存在之區域可使用當業者公知的元素分析方法來測定。具體來說，例如在作為防鏽劑含有P時，從塗膜表面朝Zn系合金鍍敷層於與塗膜表面垂直之方向上、亦即於厚度方向上進行元素分析時，可於塗膜與Zn系合金鍍層之界面附近測定到作為防鏽劑成分之P濃化的區域。並且，藉由使用當業者公知之測定原子間鍵結能之方法分析經上述方式測得之P的濃化區域，可測定防鏽劑成分的P與Zn系合金鍍層成分的Zn或Al之反應產物。The area where the reaction product exists can be determined using elemental analysis methods known to the industry. Specifically, for example, when P is contained as a rust inhibitor, elemental analysis is performed on the coating film surface in the direction perpendicular to the coating film surface toward the Zn-based alloy plating layer, that is, in the thickness direction. The area where P, which is a component of the rust inhibitor, is concentrated is measured near the interface with the Zn-based alloy coating. In addition, by analyzing the concentration area of P measured by the above method by using a method known by the industry to measure the bonding energy between atoms, the reaction between the P of the rust inhibitor component and the Zn or Al of the Zn alloy coating composition can be measured. product.

(光亮顏料) 本發明表面處理鋼板除了上述防鏽劑，為了使設計性提升，宜使光亮顏料含於塗膜中。在本說明書中使用之情況，「光亮顏料」係指可在表面反射光之顏料。此外，光亮顏料中係使用不會在用以製作塗膜之酸性塗料中溶解而可在添加至塗料中之狀態下含於塗膜中者。因此本發明中，於塗膜中「包含光亮顏料」係指將以下說明之金屬單體、氧化物或合金等含於塗膜中；於塗膜中，可明確區分光亮顏料與用來形成塗膜之黏結劑樹脂並加以特定。因此，後述光亮顏料的「濃度」係指以下說明之金屬單體、氧化物或合金等之合計濃度。(Bright pigment) In addition to the above-mentioned rust inhibitor, the surface-treated steel sheet of the present invention preferably contains bright pigments in the coating film in order to improve design. As used in this manual, "bright pigment" refers to a pigment that can reflect light on the surface. In addition, bright pigments are those that do not dissolve in the acid paint used to make the paint film, but can be contained in the paint film while being added to the paint. Therefore, in the present invention, "contains bright pigments" in the coating film means that the metal monomers, oxides, or alloys described below are contained in the coating film; in the coating film, bright pigments can be clearly distinguished from those used to form the coating. The adhesive resin of the film is specified. Therefore, the "concentration" of the bright pigment described later refers to the total concentration of metal monomers, oxides, alloys, etc. described below.

要使設計性提升之理由係因將Zn系合金鍍敷鋼板使用於建材用或屋外家電用的製品一般多用在從使用者等可目視之場所，故所述Zn系合金鍍敷鋼板宜具有良好的視覺品質(外觀)。尤其將光亮顏料設於靠近Zn系合金鍍層時，可使塗膜厚度不均不明顯或使傷痕不明顯。因此，可減薄塗膜厚度而於經濟上來說為佳。The reason for improving the design is that Zn-based alloy coated steel sheets are used in building materials or outdoor home appliances. Products are generally used in places that are visible from users, so the Zn-based alloy coated steel sheets should have good The visual quality (appearance). Especially when the bright pigment is placed close to the Zn-based alloy plating layer, the unevenness of the coating film thickness or the scars can be inconspicuous. Therefore, the thickness of the coating film can be reduced, which is economically preferable.

所以藉由將如上述之光亮顏料使用於塗膜中，可藉由其金屬外觀(例如銀色)使表面處理鋼板的亮度提升，而可提供具有優異外觀之高設計性的表面處理鋼板。並且，當光亮顏料具有與Zn系合金鍍層相同或類似色調時，於塗膜損傷時可不凸顯傷痕所致外觀變化，因此可使耐損傷性提升，而可長時間維持本發明表面處理鋼板之優異外觀。Therefore, by using the above-mentioned bright pigment in the coating film, the brightness of the surface-treated steel sheet can be improved by its metallic appearance (for example, silver), and a highly-designed surface-treated steel sheet with excellent appearance can be provided. In addition, when the bright pigment has the same or similar hue as the Zn-based alloy coating, the appearance change caused by the scar will not be highlighted when the coating film is damaged, so the damage resistance can be improved, and the excellent surface treatment steel sheet of the present invention can be maintained for a long time. Exterior.

而且，藉由光亮顏料含於塗膜中，當從與塗膜表面垂直之方向觀察本發明表面處理鋼板時，可藉由光亮顏料使基底的Zn系合金鍍層不被看見。如此一來，例如即便在Zn系合金鍍層所含Zn因空氣中的氧等影響而氧化，形成了缺氧之Zn氧化物而Zn系合金鍍層變黑時，可藉由光亮顏料使該黑變不被看見，而可維持本發明表面處理鋼板之設計性。Moreover, by the bright pigment contained in the coating film, when the surface-treated steel sheet of the present invention is viewed from a direction perpendicular to the surface of the coating film, the bright pigment can make the base Zn alloy coating invisible. In this way, for example, even if the Zn contained in the Zn-based alloy coating is oxidized due to the influence of oxygen in the air, forming an oxygen-deficient Zn oxide and the Zn-based alloy coating becomes black, the bright pigment can be used to make the black It is not seen, but the design of the surface-treated steel sheet of the present invention can be maintained.

本發明之光亮顏料只要為可於本發明所用pH3.0~5.0之酸性塗料中使用、亦即不會在該pH範圍溶解者則無特別限定，例如可使用鋁或氧化物。氧化物之例未限定，例如可舉氧化鋁、氧化矽、雲母、氧化鋯、氧化鈦、玻璃、氧化鋅等。該等顏料經以氧化矽等金屬氧化物塗覆，而具有金屬外觀(亦稱金屬感外觀)。該等可於塗膜中單獨或組合使用。The bright pigment of the present invention is not particularly limited as long as it can be used in the acid paint of pH 3.0 to 5.0 used in the present invention, that is, it does not dissolve in the pH range. For example, aluminum or oxide can be used. Examples of oxides are not limited, and examples thereof include aluminum oxide, silicon oxide, mica, zirconium oxide, titanium oxide, glass, and zinc oxide. The pigments are coated with metal oxides such as silicon oxide, and have a metallic appearance (also called metallic appearance). These can be used alone or in combination in the coating film.

作為本發明之光亮顏料，除了上述鋁或氧化物外，更可將可提供高亮度之金屬添加於塗膜中。所述金屬之例只要為具有高亮度且可在酸性塗料中使用之金屬則無特別限定，例如可舉Rh(銠)、Cr(鉻)、Ti(鈦)、Ag(銀)及Cu(銅)等金屬單體、Zn-Cu(黃銅)等合金等。該等金屬可在塗膜中單獨或組合使用。藉由將可提供所述高亮度之金屬含於塗膜中，可更提高塗膜的金屬外觀，因此可更提升本發明表面處理鋼板之亮度，而可更提升表面處理鋼板之設計性。As the bright pigment of the present invention, in addition to the above-mentioned aluminum or oxide, a metal that can provide high brightness can be added to the coating film. Examples of the metal are not particularly limited as long as they have high brightness and can be used in acid paints, such as Rh (rhodium), Cr (chromium), Ti (titanium), Ag (silver) and Cu (copper). ) And other metal monomers, Zn-Cu (brass) and other alloys. These metals can be used alone or in combination in the coating film. By including the metal that can provide the high brightness in the coating film, the metal appearance of the coating film can be further improved, so the brightness of the surface-treated steel sheet of the present invention can be further improved, and the design of the surface-treated steel sheet can be further improved.

本發明光亮顏料的平均粒徑並無特別限定，例如可為1μm以上且30μm以下之範圍。藉由光亮顏料之平均粒徑在1μm以上且30μm以下之範圍，可不致使亮度不均發生而在維持耐蝕性下提供充分的設計性。光亮顏料之平均粒徑若小於1μm，則難以使其在用以形成本發明之塗膜的塗料中均勻分散，而有所形成之塗膜色調產生不均，無法確保充分的設計性之虞。另一方面，光亮顏料之平均粒徑大於30μm時，光亮顏料會從塗膜表面突出而有腐蝕因子從該突出部分入侵之虞，從而有造成耐蝕性變差之虞。並且，當存在所述突出部分時會難以具有均勻外觀而有設計性不足之虞。光亮顏料的平均粒徑可為2μm以上或3μm以上，且可為25μm以上以下、20μm以下或15μm以下，而宜為3μm以上且25μm以下，更宜為3μm以上且20μm以下，以3μm以上且15μm以下更佳。The average particle diameter of the bright pigment of the present invention is not particularly limited, and may be, for example, a range of 1 μm or more and 30 μm or less. When the average particle diameter of the bright pigment is in the range of 1 μm or more and 30 μm or less, it is possible to prevent uneven brightness and provide sufficient design while maintaining corrosion resistance. If the average particle size of the bright pigment is less than 1 μm, it is difficult to uniformly disperse it in the coating used to form the coating film of the present invention, and the color tone of the formed coating film may be uneven, and sufficient design may not be ensured. On the other hand, when the average particle size of the bright pigment is greater than 30 μm, the bright pigment may protrude from the surface of the coating film and corrosive factors may invade from the protruding part, which may cause deterioration of corrosion resistance. In addition, when the protruding portion is present, it is difficult to have a uniform appearance, and there is a risk of insufficient design. The average particle size of the bright pigment can be 2μm or more or 3μm or more, and can be 25μm or less, 20μm or less, or 15μm or less, preferably 3μm or more and 25μm or less, more preferably 3μm or more and 20μm or less, and 3μm or more and 15μm or less The following is better.

在本說明書中使用之情況，關於本發明之光亮顏料的「平均粒徑」舉例來說可以以下方法決定。從對塗膜表面呈垂直之方向藉由場發射型電子探針微量分析儀(Field Emission-Electron Prove Micro Analyzer：FE-EPMA)求得構成光亮顏料之元素的分布影像。分布影像的測定範圍面積設為20mm×20mm以上。從所得分布影像特定出測定範圍內存在之光亮顏料的輪廓，並求出被該輪廓包圍住的合計面積S。並求出測定範圍內存在之光亮顏料的個數N。然後假設求出之面積S係由截面為具有直徑(粒徑)D之圓形的N個光亮顏料構成，從[D=2×(S/(πN))0.5 ]之式求出光亮顏料的平均粒徑。When used in this specification, the "average particle size" of the bright pigment of the present invention can be determined by the following method, for example. The distribution image of the elements constituting the bright pigment is obtained by the Field Emission-Electron Prove Micro Analyzer (FE-EPMA) in the direction perpendicular to the coating film surface. The area of the measurement range of the distributed image is set to 20mm×20mm or more. From the obtained distribution image, the outline of the bright pigment in the measurement range is specified, and the total area S surrounded by the outline is obtained. And find the number N of bright pigments in the measuring range. Then suppose that the calculated area S is composed of N bright pigments with a circular cross section of diameter (particle size) D. From the formula [D=2×(S/(πN)) 0.5 ], find the bright pigment The average particle size.

本發明之光亮顏料形狀可使用任意形狀者，例如可為球狀、楕圓狀、針狀、扁平狀、薄板狀、鱗片狀等。較佳的是光亮顏料的形狀可為鱗片狀。本發明之光亮顏料的形狀為鱗片狀時，可利用光亮顏料有效地使基底的Zn系合金鍍層不被看見，亦即可有效地抑制Zn系合金鍍層的黑變所致之製品外觀上的變化，而可提供設計性極優異之表面處理鋼板。The shape of the bright pigment of the present invention can be any shape, for example, spherical, elliptical, needle, flat, thin plate, scaly, etc. can be used. Preferably, the shape of the bright pigment may be scaly. When the shape of the bright pigment of the present invention is scaly, the bright pigment can be used to effectively make the Zn alloy coating of the substrate invisible, and it can effectively suppress the appearance change of the product caused by the blackening of the Zn alloy coating. , And can provide surface treatment steel plate with excellent design.

塗膜中之光亮顏料的平均濃度例如以質量%計可為5~15%。藉由為所述範圍之塗膜中的光亮顏料的平均濃度，可在不損塗膜加工性下對本發明表面處理鋼板提供均勻的金屬外觀，而可提供設計性佳之表面處理鋼板。塗膜中之光亮顏料的平均濃度若小於5%，則有塗膜中的光亮顏料不足而無法提供充分的金屬外觀，且亮度不充分而無法提供充分設計性之情形。另一方面，塗膜中之光亮顏料的平均濃度大於15%時，添加光亮顏料帶來的亮度提升會達飽和，而於成本上來說不佳。且塗膜中存在大量光亮顏料，會相對地使構成塗膜之黏結劑樹脂的比率降低，而有於加工時使塗膜產生龜裂等造成加工性降低之虞。較佳為塗膜中之光亮顏料的平均濃度為5%以上且12%以下、更佳為6%以上且10%以下。The average concentration of the bright pigment in the coating film may be 5-15% in terms of mass %, for example. By being the average concentration of the bright pigment in the coating film in the above range, the surface-treated steel sheet of the present invention can be provided with a uniform metallic appearance without impairing the processability of the coating film, and a surface-treated steel sheet with good design can be provided. If the average concentration of the bright pigment in the coating film is less than 5%, the bright pigment in the coating film is insufficient to provide a sufficient metallic appearance, and the brightness is insufficient to provide sufficient designability. On the other hand, when the average concentration of bright pigments in the coating film is greater than 15%, the brightness enhancement brought by the addition of bright pigments will reach saturation, which is not good in terms of cost. In addition, the presence of a large amount of bright pigments in the coating film will relatively reduce the ratio of the binder resin constituting the coating film, and may cause cracks in the coating film during processing, which may reduce the processability. Preferably, the average concentration of the bright pigment in the coating film is 5% or more and 12% or less, more preferably 6% or more and 10% or less.

在本說明書中使用之情況，「塗膜中之光亮顏料的平均濃度」可以公知方法求得。例如可使用輝光放電發光表面分析裝置(Glow Discharge Optical Emission Spectrometry：GD-OES)來測定。具體而言，在可確認光亮顏料的種類、亦即可確認光亮顏料之具體的化合物時，首先係將塗膜從表面朝Zn系合金鍍層進行濺鍍，並就構成光亮顏料之主要元素以每1.0μm測定深度方向之濃度曲線。之後，求出測得之主要元素的濃度的平均值，換算從已知之著色顏料的化合物的分子量測得之濃度，而求出塗膜中之光亮顏料的平均濃度。並以機械性或化學性方式剝離塗膜後，測定塗膜的整體質量。然後，藉由分析來測定剝離後之塗膜所含光亮顏料濃度。剝離後之塗膜中之光亮顏料的濃度的分析方法可使用例如感應電漿發光分析(Inductively Coupled Plasma：ICP)或螢光X射線分析。而在不知光亮顏料的種類、亦即不知光亮顏料之具體的化合物時，可對塗膜的截面(與塗膜表面垂直之面)藉由FE-EPMA分析構成光亮顏料之元素來特定光亮顏料的種類後，如上述來測定「塗膜中之光亮顏料的平均濃度」。當光亮顏料為屬合金的黃銅時，係以Cu與Zn含量(濃度)之合計作為塗膜中之光亮顏料的平均濃度。In the case of use in this manual, the "average concentration of bright pigment in the coating film" can be obtained by a known method. For example, it can be measured using a glow discharge optical emission surface analyzer (Glow Discharge Optical Emission Spectrometry: GD-OES). Specifically, when the type of bright pigment can be confirmed, that is, the specific compound of the bright pigment, the coating film is first sputtered from the surface to the Zn-based alloy plating layer, and the main elements constituting the bright pigment 1.0μm to measure the concentration curve in the depth direction. After that, the average concentration of the measured main elements is calculated, and the concentration measured from the molecular weight of the known coloring pigment compound is converted to obtain the average concentration of the bright pigment in the coating film. After peeling off the coating film mechanically or chemically, the overall quality of the coating film is measured. Then, the concentration of bright pigment contained in the coating film after peeling was measured by analysis. The analysis method of the concentration of the bright pigment in the coating film after peeling can use, for example, Inductively Coupled Plasma (ICP) or fluorescent X-ray analysis. When the type of bright pigment is unknown, that is, the specific compound of the bright pigment is unknown, the cross section of the coating film (the surface perpendicular to the surface of the coating film) can be analyzed by FE-EPMA to determine the composition of the bright pigment. After sorting, determine the "average concentration of bright pigment in the coating film" as described above. When the bright pigment is alloy brass, the sum of Cu and Zn content (concentration) is used as the average concentration of bright pigment in the coating film.

本發明之塗膜中亦可因應需要添加本發明之防鏽劑及光亮顏料以外之顏料或凝聚體等。又塗膜中亦可添加如聚乙烯蠟或PTFE蠟之蠟、如丙烯酸樹脂珠粒或胺甲酸乙酯樹脂珠粒之樹脂珠粒、以及如酞花青藍、酞花青綠、甲基橙、甲基紫或茜素之染料等。藉由添加該等可提高塗膜的強度、賦予塗膜所期望之顏色，故而更佳。該等添加量只要不會對本發明之塗膜造成不利即可適當決定。In the coating film of the present invention, pigments or aggregates other than the rust inhibitor and bright pigment of the present invention can also be added as needed. Also, waxes such as polyethylene wax or PTFE wax, resin beads such as acrylic resin beads or urethane resin beads, and such as phthalocyanine blue, phthalocyanine green, methyl orange, Dyes such as methyl violet or alizarin. By adding these, the strength of the coating film can be increased and the desired color can be imparted to the coating film, which is better. These addition amounts can be appropriately determined as long as they do not adversely affect the coating film of the present invention.

尤其，為了對本發明之塗膜賦予所期望之顏色、進而以賦予本發明表面處理鋼板所期望之顏色，可使用染料作為著色劑。染料可單獨使用亦可組合多種染料來使用。且可將染料與著色顏料併用。可用於本發明之塗膜中之染料的種類無特別限定，可使用公知的染料，例如可使用酞花青藍、酞花青綠、甲基橙、甲基紫或茜素。In particular, in order to impart a desired color to the coating film of the present invention, and further to impart a desired color to the surface-treated steel sheet of the present invention, a dye can be used as a colorant. The dye may be used alone or in combination of multiple dyes. And can use dyes and coloring pigments together. The types of dyes that can be used in the coating film of the present invention are not particularly limited, and well-known dyes can be used. For example, phthalocyanine blue, phthalocyanine green, methyl orange, methyl violet, or alizarin can be used.

[表面處理鋼板的製造方法] 以下說明本發明表面處理鋼板的製造方法。本發明表面處理鋼板例如可以以下方式製造：於形成於鋼板上之Zn系合金鍍層上塗佈至少包含防鏽劑與黏結劑樹脂且pH3.0~5.0之酸性塗料，並加熱使塗料硬化來製造。[Method of manufacturing surface treated steel sheet] Hereinafter, the manufacturing method of the surface-treated steel sheet of the present invention will be described. The surface-treated steel sheet of the present invention can be manufactured, for example, by applying an acid paint containing at least a rust inhibitor and a binder resin and having a pH of 3.0 to 5.0 on the Zn-based alloy plating layer formed on the steel sheet, and heating to harden the paint. .

>形成Zn系合金鍍層> 鋼板可使用具有任意板厚及化學組成者。例如可使用板厚0.25~3.5mm之冷軋鋼板。又，Zn系合金鍍層例如可使用400~550℃之Zn-Al-Mg熔融鍍敷浴或Zn-Al-Mg-Si熔融鍍敷浴以5~30μm之厚度形成。>Formation of Zn alloy coating> The steel plate can have any thickness and chemical composition. For example, cold rolled steel plates with a thickness of 0.25 to 3.5 mm can be used. In addition, the Zn-based alloy plating layer can be formed with a thickness of 5-30 μm using a Zn-Al-Mg hot-dip bath or a Zn-Al-Mg-Si hot-dip bath at 400 to 550°C.

>調製塗料> 塗料例如可以以下方式獲得：混合已分散於溶劑中之黏結劑樹脂與硬化劑，接著於該混合物中使預定量的防鏽劑源、任意選擇之光亮顏料分散而獲得。混合順序可不同。黏結劑樹脂並無特別限定，可使用聚酯樹脂、胺甲酸乙酯樹脂或丙烯酸樹脂等，而硬化劑可使用三聚氰胺樹脂等。又，溶劑係使用酸性者，防鏽劑源係使用會溶解於該酸性溶劑中者，例如可使用P化合物、V化合物、Mg化合物或其等中之2種以上。另一方面，光亮顏料可從不會在酸性溶劑中溶解之顏料適當選擇。黏結劑樹脂與硬化劑之比可適當決定，例如可為1：1~9：1之範圍。>Modulation paint> The coating material can be obtained, for example, by mixing a binder resin and a hardener dispersed in a solvent, and then dispersing a predetermined amount of a rust inhibitor source and an optionally selected bright pigment in the mixture. The mixing sequence can be different. The binder resin is not particularly limited, and polyester resin, urethane resin, acrylic resin, or the like can be used, and melamine resin or the like can be used as the hardener. In addition, the solvent is acidic, and the rust inhibitor source is soluble in the acidic solvent. For example, two or more of P compound, V compound, Mg compound, or the like can be used. On the other hand, bright pigments can be appropriately selected from pigments that will not dissolve in acid solvents. The ratio of the binder resin to the hardener can be appropriately determined, for example, it can be in the range of 1:1-9:1.

為了獲得本發明塗膜所使用之塗料的pH為3.0以上且5.0以下很是重要。藉由將塗料的pH設為所述範圍，不僅可使防鏽劑源溶解於塗料中，在將所述塗料塗佈於Zn系合金鍍層時，還可適切去除Zn系合金鍍層表面上之氧化被膜。如此一來，在Zn系合金鍍層之表面附近，離子狀態的防鏽劑成分與Zn系合金鍍層中之成分會進行反應，結果在使塗料硬化後，可於Zn系合金鍍層與塗膜之界面附近形成反應產物濃化的區域。當塗料的pH小於3.0時，防鏽劑之濃化區域的濃化程度會過高，而將表面處理鋼板加工後於防鏽劑的濃化區域會有塗膜內聚破壞之情形。如此一來，加工密著性會降低，結果有無法維持在加工部之耐蝕性以致耐蝕性不充分之虞。並且塗料中會溶出Zn而有塗料的儲存穩定性降低之虞。另一方面，塗料的pH大於5.0時，會無法充分去除Zn系合金鍍層表面上之氧化被膜，而有防鏽劑未於塗膜與Zn系合金鍍層之界面附近之區域充分濃化之虞。並且，pH為鹼性時、即大於7.0時，於作成塗料時塗料會固化(膠化)，將欠缺作為塗料之儲存穩定性，會發生使用上之問題。塗料的pH可為3.2以上或3.5以上，且可為4.8以下或4.5以下。塗料的pH宜為3.2~4.8，且宜為3.5~4.5。此外，使塗料硬化形成塗膜後將無法測定pH。In order to obtain the coating film of the present invention, it is important that the pH of the coating material used is 3.0 or more and 5.0 or less. By setting the pH of the paint in the above range, not only can the anti-rust agent source be dissolved in the paint, but also when the paint is applied to the Zn-based alloy coating, the oxidation on the surface of the Zn-based alloy coating can be appropriately removed Envelope. As a result, near the surface of the Zn-based alloy coating, the ionic state rust inhibitor component reacts with the components in the Zn-based alloy coating. As a result, after the coating is hardened, it can be used at the interface between the Zn-based alloy coating and the coating. An area where the reaction product is concentrated is formed nearby. When the pH of the coating is less than 3.0, the concentration of the concentrated area of the rust inhibitor will be too high, and the coating film may be damaged in the concentrated area of the rust inhibitor after processing the surface-treated steel sheet. As a result, the processing adhesion will be reduced, and as a result, the corrosion resistance in the processed part may not be maintained, and the corrosion resistance may be insufficient. In addition, Zn may be eluted from the paint, which may reduce the storage stability of the paint. On the other hand, when the pH of the coating is greater than 5.0, the oxide film on the surface of the Zn-based alloy coating may not be sufficiently removed, and the rust inhibitor may not be sufficiently concentrated in the area near the interface between the coating and the Zn-based alloy coating. In addition, when the pH is alkaline, that is, when it is greater than 7.0, the paint will be cured (gelled) when the paint is made, and the storage stability of the paint will be lacking, and problems in use may occur. The pH of the coating may be 3.2 or higher or 3.5 or higher, and may be 4.8 or lower or 4.5 or lower. The pH of the coating should be 3.2~4.8, and should be 3.5~4.5. In addition, the pH cannot be measured after the paint is hardened to form a coating film.

塗料的pH會有因原材料的溶劑等之製造批而改變之情形。因此，必須使用酸或鹼水溶液來調整pH。更具體而言，係測定調合塗料後的pH並因應所欲pH，在欲降低pH值時可使用鹽酸或硫酸，而在欲提高pH值時可使用氫氧化鈉水溶液等。該等酸或鹼水溶液宜在用於調整pH前稀釋後再使用。The pH of the paint may change due to the manufacturing batch of the solvent, etc. of the raw material. Therefore, an acid or alkali aqueous solution must be used to adjust the pH. More specifically, the pH of the paint is measured and the pH is adjusted according to the desired pH. When the pH is to be lowered, hydrochloric acid or sulfuric acid can be used, and when the pH is to be increased, an aqueous sodium hydroxide solution or the like can be used. These acid or alkali aqueous solutions should be diluted before use for pH adjustment.

>形成塗膜> 然後，將獲得之塗料塗佈於Zn系合金鍍層上以使塗膜成預定厚度，並烘烤使其硬化。塗料的塗佈方法無特別限定，可利用當業者公知之任意塗佈方法進行，例如可以輥塗機等來進行。烘烤可以塗料可硬化之任意加熱條件來進行，例如可以5~70℃/秒之加熱速度進行加熱成180~230℃之鋼板溫度。>Form a coating film> Then, the obtained paint is coated on the Zn-based alloy plating layer to make the coating film to a predetermined thickness, and baked to harden it. The coating method of the coating material is not particularly limited, and it can be performed by any coating method known to those in the art, for example, it can be performed by a roll coater or the like. Baking can be carried out under any heating conditions where the paint can be hardened, for example, it can be heated at a heating rate of 5~70℃/sec to a steel plate temperature of 180~230℃.

如上述，本發明表面處理鋼板中，包含例如P、V或Mg之防鏽劑在塗膜中係以微細化合物狀態存在。為了製成所述構成，本發明表面處理鋼板之製造方法中，為了使防鏽劑以離子狀態存在於塗料中，係使防鏽劑源(例如P化合物、V化合物或Mg化合物)溶解於酸性溶劑中，來調製用以形成本發明之塗膜的塗料。本發明人等發現藉由使用所述製造方法在如下方面上有利。As described above, in the surface-treated steel sheet of the present invention, the rust inhibitor containing, for example, P, V, or Mg is present in the coating film as a fine compound. In order to make the structure described above, in the method of manufacturing the surface-treated steel sheet of the present invention, in order to make the rust inhibitor exist in the paint in an ionic state, the rust inhibitor source (for example, P compound, V compound, or Mg compound) is dissolved in acid In the solvent, the paint for forming the coating film of the present invention is prepared. The inventors of the present invention found that the use of the manufacturing method is advantageous in the following points.

例如，與本發明不同，於像防鏽顏料以固體成分(例如粉末)狀態含於塗膜中時，吾等認為為了使防鏽顏料均勻分布於要形成之塗膜中，必須使防鏽顏料均勻分散於用以形成該塗膜之塗料中。而且所述製造方法中，若於塗料中添加大量防鏽顏料，則難以使防鏽顏料均勻分散於塗料中，並且，所形成之塗膜的主成分的樹脂比率會降低而有使塗膜變脆之虞，而防鏽顏料添加到塗膜中之量有其上限。且，所述塗料在使防鏽顏料分散來調製塗料後在保管塗料至使用之期間，分散狀態會變差，結果有無法獲得防鏽顏料均勻分布之塗膜等問題。For example, unlike the present invention, when the anti-rust pigment is contained in the coating film as a solid component (such as powder), we believe that in order to make the anti-rust pigment evenly distributed in the coating film to be formed, the anti-rust pigment must be Evenly dispersed in the paint used to form the coating film. Moreover, in the manufacturing method, if a large amount of anti-corrosion pigment is added to the paint, it is difficult to uniformly disperse the anti-corrosion pigment in the paint, and the resin ratio of the main component of the formed coating film will be lowered and the coating film will be changed. It may be brittle, and the amount of anti-rust pigment added to the coating film has its upper limit. In addition, after the paint is prepared by dispersing the rust preventive pigment, the dispersion state of the paint deteriorates from storage to use. As a result, there is a problem that a uniformly distributed coating film of the rust preventive pigment cannot be obtained.

再來，例如與本發明不同，以防鏽劑源使用會溶解於鹼性溶劑之化合物來調製塗膜用鹼性塗料之情形來說，當一直增加該化合物之添加量時，會有該防鏽劑源無法充分溶解而於塗料中產生固態物之情形。且有塗料於塗料保管中固化(膠化)之情形，而有在保管塗料上之塗料儲存穩定性的問題。又吾等認為即便將鹼性塗料塗佈於Zn系合金鍍層上，仍無法充分去除Zn系合金鍍層上之氧化被膜。Furthermore, for example, unlike the present invention, in the case of using a compound that is soluble in an alkaline solvent as a rust inhibitor source to prepare an alkaline paint for coating film, when the added amount of the compound is increased, there will be the The situation where the rust agent source cannot be fully dissolved and solids are produced in the paint. In addition, the paint may be cured (gelled) during the storage of the paint, and the storage stability of the paint on the storage of the paint may be problematic. We also believe that even if the alkaline paint is applied to the Zn-based alloy coating, the oxide film on the Zn-based alloy coating cannot be sufficiently removed.

另一方面，本發明中，係使用酸性塗料與作為防鏽劑源之會溶解於該塗料的化合物，使該化合物溶解於酸性塗料中。因此，就使防鏽劑成分均勻分散於塗料中來說，則無像使用粉末之防鏽顏料時之限制。所以，所述製造方法中，相較於包含粉末等之防鏽顏料的塗料，可於使防鏽劑均勻分散之狀態下將大量防鏽劑添加於塗料中。且，用以形成本發明之塗膜的pH3.0~5.0之酸性塗料即便在將防鏽劑源大量添加於塗料中，相較於鹼性塗料，塗料不易固化而具優異塗料儲存穩定性。如以上所述，用以形成本發明之塗膜的塗料可具有塗料的儲存穩定性並可添加大量防鏽劑源，結果可形成塗膜中含高濃度防鏽劑之塗膜。因此，藉由使用所述塗料來形成塗膜，可形成具有極優異之耐蝕性的表面處理鋼板。On the other hand, in the present invention, an acid paint and a compound that is soluble in the paint as a source of the rust inhibitor is used to dissolve the compound in the acid paint. Therefore, in terms of uniformly dispersing the rust inhibitor components in the paint, there is no restriction as when using powdered rust preventive pigments. Therefore, in the above-mentioned manufacturing method, a large amount of the rust inhibitor can be added to the paint in a state where the rust inhibitor is uniformly dispersed, compared to a paint containing a powder or other rust preventive pigment. Moreover, the acid paint of pH 3.0-5.0 used to form the coating film of the present invention, even if a large amount of rust inhibitor source is added to the paint, the paint is not easy to cure and has excellent paint storage stability compared to the alkaline paint. As described above, the coating used to form the coating film of the present invention can have the storage stability of the coating and can be added with a large amount of antirust agent sources, as a result, a coating film containing a high concentration of antirust agent in the coating film can be formed. Therefore, by using the paint to form a coating film, a surface-treated steel sheet having extremely excellent corrosion resistance can be formed.

並且如上述，本發明人等發現當將所述pH3.0~5.0之酸性塗料塗佈於Zn系合金鍍層上時，形成於Zn系合金鍍層表面之氧化被膜會被該塗料去除，而防鏽劑成分與Zn系合金鍍層中之成分會進行反應，結果會於塗膜與Zn系合金鍍層之界面附近之區域形成防鏽劑與Zn系合金鍍層中之金屬的反應產物(例如P與Zn之反應產物)。該氧化被膜之去除係因要塗佈於Zn系合金鍍層上之本發明所使用之塗料為酸性之故。而且，藉由去除氧化被膜，會使Zn系合金鍍層之氧化被膜下的活性金屬露出，該活性金屬會與塗膜中之防鏽劑成分進行反應，而形成上述反應產物。依上述生成之反應產物存在的區域中，防鏽劑相較於其他區域更濃化。因此，該濃化區域會作為防止腐蝕因子入侵Zn系合金鍍層的障蔽區域發揮作用，故本發明表面處理鋼板可具有極高之耐蝕性。And as mentioned above, the inventors found that when the acid paint with pH 3.0~5.0 is applied to the Zn alloy coating, the oxide film formed on the surface of the Zn alloy coating will be removed by the coating, thereby preventing rust The composition of the agent reacts with the components in the Zn-based alloy coating. As a result, the reaction product of the rust inhibitor and the metal in the Zn-based alloy coating (such as the combination of P and Zn) is formed in the area near the interface between the coating film and the Zn-based alloy coating. reaction product). The removal of the oxide film is because the paint used in the present invention to be coated on the Zn-based alloy plating layer is acidic. Moreover, by removing the oxide film, the active metal under the oxide film of the Zn-based alloy plating layer is exposed, and the active metal reacts with the rust inhibitor component in the coating film to form the above-mentioned reaction product. In the area where the reaction product generated as described above exists, the rust inhibitor is more concentrated than other areas. Therefore, the concentrated area functions as a barrier area for preventing corrosion factors from invading the Zn-based alloy coating, so the surface-treated steel sheet of the present invention can have extremely high corrosion resistance.

本發明表面處理鋼板、即距離Zn系合金鍍層與塗膜之界面10nm之位置的塗膜中之防鏽劑的濃度為塗膜中之防鏽劑的平均濃度的1.5倍以上且5.0倍以下之表面處理鋼板，可藉由以下方式製造：使用pH3.0~5.0之酸性塗料，並適當調整製造時之各種參數、例如塗料中之防鏽劑種類、防鏽劑添加量、塗料溫度、使塗料硬化時之加熱溫度及加熱時間、黏結劑樹脂與硬化劑之比及對合金鍍層之前處理等來製造。亦即藉由使用包含預定量之防鏽劑成分與任意選擇之光亮顏料的pH3.0~5.0之酸性塗料，並適當調整所述參數，藉此可調整塗膜中之防鏽劑的濃化程度，因此可製造本發明表面處理鋼板。The concentration of the rust inhibitor in the surface-treated steel sheet of the present invention, that is, the position 10nm away from the interface between the Zn alloy coating and the coating film, is 1.5 times or more and 5.0 times the average concentration of the rust inhibitor in the coating film. Surface-treated steel plates can be manufactured by the following methods: use acidic paint with pH 3.0~5.0, and appropriately adjust various parameters during manufacturing, such as the type of rust inhibitor in the paint, the amount of rust inhibitor added, the paint temperature, and the paint Manufactured by the heating temperature and heating time during hardening, the ratio of binder resin to hardener, and the pretreatment of alloy plating. That is, by using a pH 3.0-5.0 acid paint containing a predetermined amount of anti-corrosive ingredients and arbitrarily selected bright pigments, and adjusting the parameters appropriately, the concentration of the anti-corrosive in the coating film can be adjusted Therefore, the surface-treated steel sheet of the present invention can be manufactured.

並且，藉由去除Zn系合金鍍層之氧化被膜，使Zn系合金鍍層的活性金屬與塗料中之成分進行反應，會於Zn系合金鍍層與塗膜之間產生強力的化學性結合，故可獲得Zn系合金鍍層與塗膜間具優異密著性的表面處理鋼板。更詳細來說，不受特定理論拘束，塗料中之防鏽劑成分會進行反應而形成氫氧化物，該氫氧化物之官能基會與樹脂進行反應而產生不可逆且為化學性之結合，結果於Zn系合金鍍層與塗膜之間密著性會提升。所述密著性在例如於形成塗膜時使用中性或鹼性塗料時無法達成，因此為了形成塗膜而於使用了pH3.0~5.0之酸性塗料時，密著性會較使用中性或鹼性塗料之情形更提升。In addition, by removing the oxide film of the Zn-based alloy plating layer, the active metal of the Zn-based alloy plating layer reacts with the components in the paint, and a strong chemical bond between the Zn-based alloy plating layer and the coating film will be produced, so it can be obtained A surface-treated steel sheet with excellent adhesion between the Zn alloy coating and the coating film. In more detail, without being bound by a specific theory, the rust inhibitor component in the coating will react to form a hydroxide, and the functional group of the hydroxide will react with the resin to produce an irreversible and chemical bond. The adhesion between the Zn alloy plating layer and the coating film will improve. The above-mentioned adhesion cannot be achieved when, for example, a neutral or alkaline paint is used to form a coating film. Therefore, when an acidic paint with a pH of 3.0 to 5.0 is used to form a coating film, the adhesion will be more neutral Or the situation of alkaline paint has improved.

藉由使用如上述之製造方法，可製造本發明表面處理鋼板。亦即可製造以下表面處理鋼板：其具有鋼板、形成於鋼板之至少單面的Zn系合金鍍層及形成於Zn系合金鍍層上的塗膜，且該塗膜包含防鏽劑與黏結劑樹脂；並且，距離Zn系合金鍍層與塗膜之界面10nm之位置的塗膜中之防鏽劑濃度係塗膜中之防鏽劑的平均濃度的1.5倍以上且5.0倍以下。 實施例By using the manufacturing method as described above, the surface-treated steel sheet of the present invention can be manufactured. That is, the following surface-treated steel sheet can be manufactured: it has a steel sheet, a Zn-based alloy coating layer formed on at least one side of the steel sheet, and a coating film formed on the Zn-based alloy coating layer, and the coating film includes a rust inhibitor and a binder resin; In addition, the concentration of the rust inhibitor in the coating film at a position 10 nm from the interface between the Zn-based alloy plating layer and the coating film is 1.5 times or more and 5.0 times or less of the average concentration of the rust inhibitor in the coating film. Example

本例中，係針對將塗膜中之防鏽劑的平均濃度及濃度分布、光亮顏料的平均濃度、防鏽劑及光亮顏料的種類、黏結劑樹脂的種類以及Zn系合金鍍層之化學組成進行各種變更而製出之表面處理鋼板，評估該等之耐蝕性、亮度、加工密著性及儲存穩定性。此外，以下舉諸例詳細說明本發明表面處理鋼板。惟，非意於以以下說明之特定例限制申請專利範圍所記載之本發明之範圍。In this example, the average concentration and concentration distribution of the rust inhibitor in the coating film, the average concentration of bright pigments, the types of rust inhibitors and bright pigments, the types of binder resins, and the chemical composition of the Zn alloy coating The surface-treated steel plates produced by various changes are evaluated for their corrosion resistance, brightness, processing adhesion and storage stability. In addition, the surface-treated steel sheet of the present invention will be described in detail below with examples. However, the specific examples described below are not intended to limit the scope of the invention described in the scope of the patent application.

>製作表面處理鋼板的試料> (形成Zn系合金鍍層) 將厚度1mm之冷軋鋼板浸漬於化學組成為Al：約11%、Mg：約3%及Zn：約86%之約450℃的熔融鍍敷浴中3~5秒鐘，而於冷軋鋼板上形成約10μm厚度之Zn-11%Al-3%Mg合金鍍層。然後，變更熔解鍍敷浴的組成，以相同程序而於冷軋鋼板上形成約10μm厚度之Zn-1%Al-1%Mg合金鍍層及Zn-40%Al-8%Mg合金鍍層。或是將厚度1mm之冷軋鋼板浸漬於化學組成為Al：約11%、Mg：約3%、Si：約1%及Zn：約85%之約450℃的熔融鍍敷浴中3~5秒鐘，而於冷軋鋼板上形成約10μm厚度之Zn-11%Al-3%Mg-1%Si合金鍍層。然後，變更熔解鍍敷浴的組成，以相同程序而於冷軋鋼板上形成約10μm厚度之Zn-11%Al-3%Mg-0.4%Si合金鍍層及Zn-11%Al-3%Mg-1.5%Si合金鍍層。>Production of samples for surface treatment steel plates> (Formation of Zn alloy coating) A cold-rolled steel sheet with a thickness of 1mm is immersed in a molten coating bath of about 450°C with a chemical composition of Al: about 11%, Mg: about 3%, and Zn: about 86% for 3 to 5 seconds, and the cold-rolled steel sheet A Zn-11%Al-3%Mg alloy coating with a thickness of about 10μm is formed on the surface. Then, the composition of the melting plating bath is changed, and a Zn-1%Al-1%Mg alloy coating layer and a Zn-40%Al-8%Mg alloy coating layer with a thickness of about 10μm are formed on the cold rolled steel sheet by the same procedure. Or immerse a cold-rolled steel sheet with a thickness of 1mm in a hot-dip coating bath of about 450°C with a chemical composition of Al: about 11%, Mg: about 3%, Si: about 1%, and Zn: about 85%. In seconds, a Zn-11%Al-3%Mg-1%Si alloy coating with a thickness of about 10μm is formed on the cold rolled steel sheet. Then, the composition of the melting plating bath was changed, and a Zn-11%Al-3%Mg-0.4%Si alloy coating and Zn-11%Al-3%Mg- with a thickness of about 10μm were formed on the cold-rolled steel sheet by the same procedure. 1.5% Si alloy coating.

(調製塗料) 針對試料No.3~21及25~36使用之塗料，使用硝酸或氫氧化鈉調整成pH為3.0~5.0，該等例之塗料係使作為黏結劑樹脂之聚酯樹脂(分子量：16,000；玻璃轉移點：10℃)及聚胺甲酸乙酯樹脂(分子量：10000；玻璃轉移點：20℃)於酸性溶劑中分散成乳液狀態而成。並於其中混合亞胺基型三聚氰胺樹脂。聚酯樹脂與三聚氰胺樹脂之濃度比為100：20。接著，於該混合物中添加防鏽劑源及光亮顏料而調製出塗料。此外，針對試料No.1、2及24使用之塗料將pH調整成大於5.0，且針對試料No.22及23使用之塗料將pH調整成小於3.0。將各試料使用之塗料的pH示於表1。然後，No.25未添加光亮顏料。關於作為防鏽劑包含P、V及Mg之試料的防鏽劑源分別使用了正磷酸、五氧化釩及硫酸鎂。光亮顏料係使用表1記載之物。(Modified paint) For the paints used in sample Nos. 3-21 and 25-36, use nitric acid or sodium hydroxide to adjust the pH to 3.0-5.0. The paints in these examples use polyester resin (molecular weight: 16,000; glass) as the binder resin. Transition point: 10°C) and polyurethane resin (molecular weight: 10000; glass transition point: 20°C) dispersed in an acidic solvent into an emulsion state. And mixed with imine-based melamine resin. The concentration ratio of polyester resin to melamine resin is 100:20. Next, a rust inhibitor source and a bright pigment are added to the mixture to prepare a paint. In addition, the pH of the paint used for sample Nos. 1, 2 and 24 was adjusted to greater than 5.0, and the pH of the paint used for sample Nos. 22 and 23 was adjusted to less than 3.0. Table 1 shows the pH of the paint used for each sample. Then, No. 25 did not add bright pigments. Regarding the rust inhibitor source of the sample containing P, V, and Mg as the rust inhibitor, orthophosphoric acid, vanadium pentoxide, and magnesium sulfate were used, respectively. For the bright pigments, the ones described in Table 1 were used.

防鏽劑源添加於塗料中之添加量基於所製得之塗膜的截面使用TEM-EDS測定時，係適當調整成可得所期望之塗膜中的防鏽劑的平均濃度(3%、5%、10%、13%或15%)。又，光亮顏料的濃度使用GD-OES測定時係適當調整成平均濃度成為10%或5%。The amount of rust inhibitor source added to the paint is based on the cross-section of the coating film produced. When measured by TEM-EDS, it is appropriately adjusted to obtain the desired average concentration of the rust inhibitor in the coating film (3%, 5%, 10%, 13% or 15%). In addition, when the concentration of the bright pigment is measured using GD-OES, it is appropriately adjusted so that the average concentration becomes 10% or 5%.

(形成塗膜) 將上述調製出之塗料以形成之塗膜的平均厚度成為5μm之方式塗佈於Zn系合金鍍層上，並烘烤使其硬化。烘烤係設約20℃/秒之加熱速度及約200℃之鋼板溫度進行至塗料完全硬化為止。(Form coating) The paint prepared above was applied on the Zn-based alloy plating layer so that the average thickness of the formed coating film became 5 μm, and baked to harden it. Baking is performed with a heating rate of about 20°C/sec and a steel plate temperature of about 200°C until the paint is completely hardened.

距離Zn系合金鍍層與塗膜之界面10nm之位置的塗膜中之防鏽劑的濃度相對於塗膜中之防鏽劑的平均濃度之比可藉由適當調整塗料的pH來調整。The ratio of the concentration of the rust inhibitor in the coating film at a position 10 nm from the interface between the Zn-based alloy coating and the coating film to the average concentration of the rust inhibitor in the coating film can be adjusted by appropriately adjusting the pH of the coating.

從所製得之塗膜使用TEM-EDS進行元素分析，藉此決定塗膜中之防鏽劑的平均濃度(質量%)；及距離Zn系合金鍍層與塗膜之界面10nm之位置的塗膜中之防鏽劑的濃度相對於其平均濃度之比。並將依上述決定出之值示於表1。並將塗膜中所含防鏽劑及光亮顏料的種類示於表1。此外，塗膜中包含2種防鏽劑時，2個防鏽劑的平均濃度合計係對應表中記載之平均濃度，而各防鏽劑在塗膜中係等量存在。針對光亮顏料亦同。TEM-EDS is used to perform elemental analysis from the prepared coating film to determine the average concentration (mass %) of the rust inhibitor in the coating film; and the coating film at a distance of 10nm from the interface between the Zn alloy coating and the coating film The ratio of the concentration of the rust inhibitor to its average concentration. And the values determined based on the above are shown in Table 1. Table 1 shows the types of rust inhibitor and bright pigment contained in the coating film. In addition, when two types of rust inhibitors are contained in the coating film, the total average concentration of the two rust inhibitors is the average concentration described in the corresponding table, and each rust inhibitor is present in the coating film in equal amounts. The same applies to bright pigments.

>評估表面處理鋼板的試料> 如上述做出表面處理鋼板之試料，並就如表1所示之各試料如下進行耐蝕性、亮度、加工密著性及儲存穩定性之評估試驗。>Evaluation of samples for surface-treated steel plates> Samples of surface-treated steel plates were made as described above, and evaluation tests of corrosion resistance, brightness, processing adhesion, and storage stability were performed for each sample shown in Table 1 as follows.

(耐蝕性的評估試驗) 針對各試料，利用依模擬實際使用之依契遜試驗(JIS Z2247：2006)的加工(擠製成7mm)獲得試驗用之0.6mm的供試材，並對該供試材進行鹽水噴霧試驗(依循JASO M609-91法)作為耐蝕性的評估試驗。該鹽水噴霧試驗係以(1)鹽水噴霧2小時(5%NaCl、35℃)；(2)乾燥4小時(60℃)；及(3)濕潤2小時(50℃、濕度95%以上)為1循環，合計實施120循環(合計960小時)。為了防止從端面腐蝕，各試料之端面係用膠帶密封後進行了試驗。(Evaluation test of corrosion resistance) For each sample, the 0.6mm test material was obtained by processing (extruded to 7mm) according to the Ichison test (JIS Z2247: 2006) according to the actual use of the simulation, and the salt spray test ( Follow JASO M609-91 method) as the evaluation test of corrosion resistance. The salt water spray test is based on (1) salt water spray for 2 hours (5%NaCl, 35°C); (2) drying for 4 hours (60°C); and (3) wetting for 2 hours (50°C, humidity above 95%) 1 cycle, 120 cycles in total (960 hours in total). In order to prevent corrosion from the end face, the end face of each sample was sealed with tape and tested.

耐蝕性之評估係使用光學顯微鏡觀察鹽水噴霧試驗960小時後之試料表面(平面部)，來確認產生鏽之面積率Z而進行。具體而言，首先用掃描器讀取試料表面。然後，用影像編輯軟體選擇有產生鏽之區域，並求出產生鏽之面積率。對5個試料進行該程序，將產生鏽之面積率的平均決定為「產生鏽之面積率Z」。並按經以上述方法對各試料決定出之「產生鏽之面積率Z」，依以下方式以8階段決定各試料之評分。以評分4以上作為耐蝕性的合格分數。 評分8：Z＝0% 評分7：0%>Z≦5% 評分6：5%>Z≦10% 評分5：10%>Z≦20% 評分4：20%>Z≦30% 評分3：30%>Z≦40% 評分2：40%>Z≦50% 評分1：50%>ZThe corrosion resistance was evaluated by observing the sample surface (flat part) after 960 hours of the salt spray test with an optical microscope to confirm the area ratio Z where rust occurred. Specifically, first, the surface of the sample is read with a scanner. Then, use the image editing software to select the area where rust occurs, and calculate the area rate of rust. This procedure was performed on 5 samples, and the average of the area rate of rust was determined as the "area rate of rust Z". And according to the "Rust Area Rate Z" determined by the above method for each sample, the score of each sample is determined in 8 stages in the following manner. A score of 4 or more is regarded as the pass score for corrosion resistance. Score 8: Z=0% Rating 7: 0%>Z≦5% Score 6: 5%>Z≦10% Rating 5: 10%>Z≦20% Rating 4: 20%>Z≦30% Score 3: 30%>Z≦40% Rating 2: 40%>Z≦50% Rating 1: 50%>Z

(亮度之評估試驗) 針對各試料，使隨機選出之10名試驗者以目視觀察試料表面，並如下以1分至5分評估「亮度程度」。 1分：完全沒確認到金屬外觀或有確認到些微金屬外觀 2分：有確認到金屬外觀，但從前視觀察時易確認到外觀不均 3分：有確認到金屬外觀，但從前視觀察時有確認到些微外觀不均 4分：有確認到整體金屬外觀，但從斜向觀察時確認到些微外觀不均 5分：有確認到整體金屬外觀(Brightness evaluation test) For each sample, 10 randomly selected testers visually observe the surface of the sample, and evaluate the "brightness level" from 1 to 5 points as follows. 1 point: No metal appearance or slight metal appearance is confirmed 2 points: Metal appearance is confirmed, but uneven appearance is easy to confirm when observed from the front view 3 points: Metal appearance is confirmed, but slight uneven appearance is confirmed when observed from the front view 4 points: The overall metal appearance is confirmed, but slight unevenness in appearance is confirmed when viewed obliquely 5 points: The overall metal appearance is confirmed

關於亮度，係依上述10名試驗者的「亮度程度」的合計分數，如下以8階段決定各試料的評分。以評分4以上作為亮度的合格分數。 評分8：40＜合計分數 評分7：35＜合計分數≦40 評分6：30＜合計分數≦35 評分5：25＜合計分數≦30 評分4：20＜合計分數≦25 評分3：15＜合計分數≦20 評分2：10＜合計分數≦15 評分1：合計分數＝10Regarding the brightness, based on the total scores of the "brightness level" of the above 10 testers, the score of each sample was determined in 8 steps as follows. A score of 4 or more is regarded as the passing score for brightness. Score 8: 40 <Total score Rating 7: 35＜total score≦40 Score 6: 30＜total score≦35 Score 5: 25＜total score≦30 Rating 4: 20＜total score≦25 Score 3: 15＜total score≦20 Score 2: 10＜total score≦15 Score 1: Total score = 10

(加工密著性之評估試驗) 如上述，利用依模擬實際使用之依契遜試驗(JIS Z2247：2006)的加工(擠製成7mm)獲得試驗用之0.6mm的供試材。針對該供試材使寬度24mm的玻璃紙黏著膠帶(NICHIBAN公司製玻璃紙膠帶：註冊商標)密著於塗膜後，以45度的角度急遽剝除。從剝離後的塗膜面積求出剝離面積率Z’，並依以下基準進行評估。 評分5：0%(無剝離)＜Z’≦5% 評分4：5%＜Z’≦10% 評分3：10%＜Z’≦30% 評分2：30%＜Z’≦50% 評分1：50%＜Z’(Evaluation test of processing adhesion) As mentioned above, the 0.6mm test material for the test was obtained by processing (extruded to 7mm) according to the Ichson test (JIS Z2247: 2006) according to the actual use of the simulation. With respect to the test material, a cellophane adhesive tape (cellophane tape manufactured by NICHIBAN Corporation: registered trademark) with a width of 24 mm was adhered to the coating film, and then peeled off at an angle of 45 degrees. The peeling area ratio Z'was obtained from the area of the coating film after peeling, and evaluated based on the following criteria. Rating 5: 0% (no peeling) <Z’≦5% Rating 4: 5%＜Z’≦10% Score 3: 10%＜Z’≦30% Score 2: 30%＜Z’≦50% Rating 1: 50%＜Z’

(儲存穩定性之評估試驗) 將經以表1記載的pH調製出之塗料100g維持在25℃，並浸漬Zn-11%Al-3%Mg合金鍍敷鋼板。目視觀察浸漬60分鐘過後之塗料，就因應塗料浸漬前(調製塗料時)與浸漬後之狀態，如下決定各試料的儲存穩定性的評分。以評分3以上作為儲存穩定性的合格分數。 評分5：在鋼板浸漬前後無確認到塗料產生變化 評分4：在鋼板浸漬前後確認到塗料有變色或黏度增大中之一項 評分3：在鋼板浸漬前後確認到塗料有變色及黏度增大兩項 評分2：塗料於鋼板浸漬後固化(膠化) 評分1：於浸漬前(調製塗料時)固化(膠化)(Evaluation test of storage stability) 100 g of the paint prepared with the pH described in Table 1 was maintained at 25° C., and Zn-11%Al-3%Mg alloy plated steel sheet was immersed. By visually observing the paint after 60 minutes of immersion, according to the state of the paint before immersion (when preparing the paint) and after immersion, the storage stability score of each sample was determined as follows. A score of 3 or more is used as the pass score for storage stability. Score 5: No change in paint is confirmed before and after steel immersion Score 4: One of the color changes or viscosity increase of the paint is confirmed before and after the steel plate is immersed Score 3: Discoloration and viscosity increase of the paint are confirmed before and after the steel plate is immersed Score 2: The coating is cured (gelled) after immersing the steel plate Score 1: Curing (gelling) before dipping (when preparing paint)

針對表面處理鋼板的試料，依上述進行耐蝕性、亮度、加工密著性及儲存穩定性的評估試驗，決定各自評分。將所得結果顯示於表1。For the surface-treated steel samples, the corrosion resistance, brightness, processing adhesion, and storage stability are evaluated according to the above-mentioned tests, and their respective scores are determined. The results obtained are shown in Table 1.

[表1]

Figure 02_image001
[Table 1]
Figure 02_image001

試料No.1及2之塗料的pH高，且距離Zn系合金鍍層與塗膜之界面10nm之位置的防鏽劑的濃度相對於塗膜中之防鏽劑的平均濃度之比小於1.5，故防鏽劑濃化不充分，而濃化區域無法充分發揮保護Zn系合金鍍層的障蔽層之作用，從而耐蝕性不充分。又，試料No.22及23之塗料的pH低，且距離Zn系合金鍍層與塗膜之界面10nm之位置的防鏽劑的濃度相對於塗膜中之防鏽劑的平均濃度之比大於5.0，故耐蝕性不充分。吾等認為其係因為了獲得供試材而進行加工後，於防鏽劑之濃化區域中塗膜會內聚破壞，使加工密著性降低，結果在加工部之耐蝕性變差之故。試料No.24之塗料的pH為鹼性，而於調製塗料時塗料固化而無法形成塗膜，故無法進行耐蝕性、亮度及加工密著性之評估。The coatings of sample Nos. 1 and 2 have high pH, and the ratio of the concentration of the rust inhibitor at a position 10 nm away from the interface between the Zn-based alloy coating and the coating film to the average concentration of the rust inhibitor in the coating film is less than 1.5, so The rust inhibitor is not sufficiently concentrated, and the concentrated area cannot fully play the role of the barrier layer that protects the Zn-based alloy coating, resulting in insufficient corrosion resistance. In addition, the coatings of sample Nos. 22 and 23 have low pH, and the ratio of the concentration of the rust inhibitor at a position 10 nm away from the interface between the Zn-based alloy plating layer and the coating film to the average concentration of the rust inhibitor in the coating film is greater than 5.0 , So the corrosion resistance is insufficient. We believe that it is because after the test material is obtained and processed, the coating film will cohesively break in the concentrated area of the rust inhibitor, which will reduce the processing adhesion and result in the deterioration of the corrosion resistance of the processed part. . The pH of the paint of sample No. 24 is alkaline, and when the paint is prepared, the paint is cured and a coating film cannot be formed. Therefore, the corrosion resistance, brightness, and processing adhesion cannot be evaluated.

另一方面，試料No.3~21、No.25~36中，距離Zn系合金鍍層與塗膜之界面10nm之位置的防鏽劑的濃度相對於塗膜中之防鏽劑的平均濃度之比為1.5以上且5.0以下，故具有優異之耐蝕性。尤其作為防鏽劑含有P及V中之任一者或兩者之試料具有更優異之耐蝕性。On the other hand, in sample Nos. 3 to 21 and Nos. 25 to 36, the concentration of the rust inhibitor at a position 10 nm away from the interface between the Zn-based alloy coating and the coating film is relative to the average concentration of the rust inhibitor in the coating film The ratio is 1.5 or more and 5.0 or less, so it has excellent corrosion resistance. In particular, the sample containing either or both of P and V as a rust inhibitor has more excellent corrosion resistance.

然後，除試料No.25外之任一試料因塗膜中含有光亮顏料故皆具有充分的亮度。並且，光亮顏料含有鋁(Al)及氧化物(SiO2 、氧化鋁、雲母)中之任一者或兩者之試料具有更優異之亮度。尤其，除Al或SiO2 ，還於塗膜中含有可使塗膜中具有高亮度之金屬Rh、Ti或Ag之試料，具有極高之亮度。Then, any sample except sample No. 25 had sufficient brightness due to the bright pigment contained in the coating film. In addition, samples containing either or both of aluminum (Al) and oxides (SiO 2 , alumina, mica) have more excellent brightness. In particular, in addition to Al or SiO 2 , the coating film also contains a sample of metal Rh, Ti, or Ag that can make the coating film have high brightness, which has extremely high brightness.

試料No.14~17及No.35係變更了塗膜中之防鏽劑的平均濃度之試料。任一試料皆具有充分的耐蝕性。Sample Nos. 14 to 17 and No. 35 are samples in which the average concentration of the rust inhibitor in the coating film is changed. Any sample has sufficient corrosion resistance.

產業上之可利用性 根據本發明，因於Zn系合金鍍層與塗膜之界面附近具有防鏽劑的濃化區域，故可提供具有高耐蝕性之表面處理鋼板。藉此，作為建材或家電用之製品使用的鋼板可提供充分之耐蝕性及設計性，因此本發明可謂在產業上價值極高之發明。Industrial availability According to the present invention, since there is a concentrated area of the rust inhibitor near the interface between the Zn-based alloy plating layer and the coating film, a surface-treated steel sheet with high corrosion resistance can be provided. As a result, steel sheets used as products for building materials or home appliances can provide sufficient corrosion resistance and design properties. Therefore, the present invention can be described as an invention with extremely high industrial value.

Claims (7)

一種表面處理鋼板，其特徵在於：具有鋼板、形成於前述鋼板之至少單面的Zn系合金鍍層及形成於前述Zn系合金鍍層上的塗膜，且該塗膜包含防鏽劑與黏結劑樹脂；前述Zn系合金鍍層之化學組成以質量%計為：Al：0.01~60%、Mg：0.001~10%及Si：0~2%；並且前述防鏽劑為P、V及Mg中之至少1種，前述塗膜中之P、V及Mg之合計的平均濃度以質量%計為3~15%；並且距離前述Zn系合金鍍層與前述塗膜之界面10nm之位置的前述塗膜中之前述防鏽劑的濃度，係前述塗膜中之前述防鏽劑的平均濃度的1.5~5.0倍。 A surface-treated steel sheet, characterized by having a steel sheet, a Zn-based alloy coating layer formed on at least one side of the aforementioned steel sheet, and a coating film formed on the aforementioned Zn-based alloy coating layer, and the coating film includes a rust inhibitor and a binder resin ; The chemical composition of the aforementioned Zn-based alloy coating is calculated by mass %: Al: 0.01~60%, Mg: 0.001~10% and Si: 0~2%; and the aforementioned rust inhibitor is at least one of P, V and Mg One type, the total average concentration of P, V, and Mg in the coating film is 3-15% by mass; and in the coating film at a position 10nm away from the interface between the Zn-based alloy coating and the coating film The concentration of the rust inhibitor is 1.5 to 5.0 times the average concentration of the rust inhibitor in the coating film. 如請求項1之表面處理鋼板，其中前述塗膜中之P、V及Mg之合計的平均濃度以質量%計為5~15%。 Such as the surface treatment steel sheet of claim 1, wherein the total average concentration of P, V and Mg in the aforementioned coating film is 5-15% by mass%. 如請求項1之表面處理鋼板，其中前述塗膜更包含光亮顏料，且前述光亮顏料包含鋁及氧化物中之至少1種。 The surface-treated steel sheet according to claim 1, wherein the coating film further contains a bright pigment, and the bright pigment contains at least one of aluminum and oxide. 如請求項3之表面處理鋼板，其中前述氧化物為氧化鋁、氧化矽、雲母、氧化鋯、氧化鈦、玻璃或氧化鋅。 Such as the surface-treated steel sheet of claim 3, wherein the aforementioned oxide is aluminum oxide, silicon oxide, mica, zirconium oxide, titanium oxide, glass or zinc oxide. 如請求項3之表面處理鋼板，其中前述光 亮顏料更包含Rh、Cr、Ti、Ag及Cu中之至少1種。 Such as the surface treatment steel plate of claim 3, wherein the aforementioned light Bright pigments further include at least one of Rh, Cr, Ti, Ag and Cu. 如請求項3之表面處理鋼板，其中前述塗膜中之前述光亮顏料的平均濃度以質量%計為5~15%。 Such as the surface treatment steel sheet of claim 3, wherein the average concentration of the bright pigment in the coating film is 5-15% by mass%. 如請求項1至6中任一項之表面處理鋼板，其中前述黏結劑樹脂為聚酯樹脂。 The surface-treated steel sheet according to any one of claims 1 to 6, wherein the aforementioned binder resin is a polyester resin.
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